Carbon Dioxide Methanol Research Articles

Optimization of methanol yield and carbon dioxide utilization in methanol synthesis process

The method of CO2 hydrogenation to methanol can effectively reduce carbon emission and has wide application prospects in chemical industry and environment. Therefore, methanol synthesis is an important way to save energy, reduce emission and transform energy utilization. In this paper, the mathematical model of methanol synthesis reactor is established. Under the condition of controllable cooling temperature, the optimization is carried out with maximum methanol yield and CO2 utilization rate. The results show that the methanol yield can be increased by 6.57% and CO2 utilization rate can be increased to 39.1% by adjusting the cooling temperature control strategy. The comparative study found that the optimal cooling temperatures all show up and down variations, with local minima and maxima. In addition, an industrial application method of methanol yield maximization cooling strategy is proposed. When the stage cooling at different temperatures is adopted, the methanol yield could be increased by 5.38%.

Unveiling the inherent properties and impact of ultrafine nanobubbles in polar and alcoholic media through unsupervised machine learning and atomic insight

The presence of dissolved gas in the host medium in various industrial processes, such as the presence of oxygen and hydrogen during water splitting or carbon dioxide in fuel cells, or the dissolution of nitrogen for industrial applications, increases the probability of the formation of bubbles at nano-scale. Nanobubbles (NBs), spanning tens to hundreds of nanometres, display exceptional attributes, including remarkable stability, enduring longevity, and an impressive surface-to-volume ratio. These qualities firmly position NBs as pivotal entities with applications that extend across diverse industries, encompassing fields such as energy and chemistry. Therefore, it is crucial to have a comprehensive understanding of their inherent properties and behaviour right from the nucleation stage to grasp their distinctive traits fully. This paper focuses on the combination of data-driven and molecular dynamics simulation to provide a clear understanding of the mechanisms behind NBs nucleation and behaviour in liquids and identify their characteristics. The nucleation process of four gases in two potential liquids for hosting NBs, namely water and methanol, was investigated through scattering nitrogen, oxygen, carbon dioxide, and hydrogen in host liquids using molecular dynamics simulations. Then, high-throughput screening based on the DBSCA (density-based spatial clustering of applications with noise) algorithm was used to screen the formed NB clusters through dissolved gases in the host liquids to determine the size of formed NBs, their density, and motion over time. The findings offer unique insights, indicating that the density of the surrounding liquids is altered and decreased by formed nanobubbles, influenced by the establishment of a nanolayer. The lowest density was recorded for hydrogen and nitrogen nanobubbled methanol samples at 0.61673 and 0.68918 g/ml, respectively, and for hydrogen and nitrogen nanobubbled water samples at 0.93797 and 0.93722 g/ml, respectively. Additionally, the highest density among the scattered gases was observed in non-nanobubbled carbon dioxide methanol and water samples at 0.77724 and 0.99588 g/ml, respectively. Furthermore, the viscosity of the host liquids is influenced, particularly in the presence of high-density nanobubbles, as the highest viscosity was observed for nitrogen nanobubbled water samples at 0.00103 Pa.s.

Rapid determination of impurities in carbon dioxide for food by gas chromatography

This article describes the experimental principle and method of rapid determination of carbon monoxide, methane, propane, total hydrocarbon, methanol, ethylene oxide, acetaldehyde, vinyl chloride, benzene, and other common impurities in carbon dioxide by gas chromatograph. By using food additive carbon dioxide as a sample, the rapid analysis conditions, such as chromatographic column, valve switching time, and column box temperature control, were optimized. The retention time of impurity components in food additive carbon dioxide was determined using the external standard method. The relative standard uncertainty of CH4, C3H8, CO, CH3OH, CH2CH2O, CH3CHO, CH2CHCl, and C6H6 analysis is within 3% by using the established analytical method proposed in this article, which is equivalent to the national standard GB 1886.228-2016. The linear correlation coefficient r is greater than 0.9995, and the linear error is not greater than 2.0, indicating excellent linearity. In the meantime, in the case of 6 consecutive sample injections, the detection time is shortened by nearly three times. The experimental results show that the analytical method established in this article is suitable for the rapid determination of impurities in carbon dioxide for food, which can improve the accuracy of experimental results and work efficiency.

Heterogeneous catalysts, reaction kinetics, and reactor designs for methanol production from carbon dioxide: A critical review

AbstractThe process of preparing methanol from carbon dioxide is one of the ways to solve the environmental problems caused by greenhouse gases, the problem of fossil energy depletion, and the problem of fuel exhaust emissions. However, after decades of development, the process of preparing methanol from carbon dioxide is still unable to achieve large‐scale industrialization. This critical review sharply points out the problems and obstacles that need to be solved urgently on the industrialization road of carbon dioxide methanol preparation process and summarizes its progress. The problems faced by the methanol production industry from carbon dioxide are first the thermodynamic constraints, second the lower reaction rate and conversion effect, and finally the energy loss. In order to solve these problems, this paper first introduces the active sites, structural effects, and dynamic changes of copper‐based catalysts, as well as the unique reaction mechanism and doping modification of indium‐based catalysts. Zinc and zirconium promoters and some metal oxide supports can form unique interactions with active components to improve the catalytic performance of the catalyst. Next, various kinetic models and applications of methanol production from carbon dioxide are summarized, which is an important bridge linking laboratory and industrialization; the advantages and disadvantages of fixed bed reactor and paddle reactor were compared. Finally, the full text is summarized and prospected.

Analytical and Preparative Separation of Softwood Lignans by Supercritical Fluid Chromatography

Lignans are widespread polyphenolic secondary plant metabolites possessing high biological activity. One of the most promising industrial-scale sources of such compounds is coniferous knotwood, containing a large number of polyphenolic compounds. Their use in pharmaceutical and other industries is limited by the difficulty in obtaining high-purity preparations from plant material and the requirement of advanced separation techniques. In this study, supercritical fluid chromatography on polar stationary phases was proposed for the efficient separation and identification of spruce, pine, fir, and larch knotwood extractives. Among the six tested sorbents, the best results were shown by silica with grafted diol and 2-ethylpyridine groups under conditions of gradient elution with a carbon dioxide–methanol mobile phase, which ensured the efficient retention and separation of analytes due to donor–acceptor interactions. Scaling up the method on a DIOL stationary phase provided a semi-preparative separation of extractives within 30 min to obtain 14 individual compounds with a purity of 90–99% and yields from 0.3 to 51% of the dry extract. These included eight lignans (nortrachelogenin, matairesinol, oxomatairesinol, α-conidendrin, 5-hydroxymatairesinol and its isomer, lariciresinol, and secoisolariciresinol), two oligolignans, three stilbenes (pinosylvin and its methyl ester, pterostilbene), and flavonoid taxifolin. The developed approach is distinguished with low operational costs, low consumption of organic solvents, environmental safety, and it is fully consistent with the principles of green chemistry.

Experimental Determination of a Chiral Ternary Solubility Diagram and Its Interpretation in Gas Antisolvent Fractionation

Although crystallization has been widely applied for the enantiomeric enrichment of non-racemates both in research and in industrial applications, the physical-chemical background of chiral crystallizations is not as frequently discussed. A guide for the experimental determination of such phase equilibrium information is lacking. In the current paper, the experimental investigation of chiral melting phase equilibria, chiral solubility phase diagrams and their application in atmospheric and supercritical carbon dioxide-assisted enantiomeric enrichment is described and compared. Benzylammonium mandelate is a racemic compound; it shows eutectic behavior when molten. A similar eutonic composition was observed in its methanol phase diagram at 1 °C. The influence of the ternary solubility plot could be unequivocally discovered in atmospheric recrystallization experiments, which proved that the crystalline solid phase and the liquid phase were in an equilibrium. The interpretation of the results obtained at 20 MPa and 40 °C, using the methanol-carbon dioxide mixture as a pseudo-component, was more challenging. Although the eutonic composition was found to be the limiting enantiomeric excess value in this purification process as well, the high-pressure gas antisolvent fractionation results were only clearly thermodynamically controlled in certain concentration ranges.

Investigation of the effects of purge gas recycling for increasing methanol production and carbon dioxide reduction on the environment using dynamic simulation

Nowadays, not only development but also survival requires energy. In today’s world, this energy is supplied through various carriers such as oil, gas, electricity, and renewable energy. Due to the increasing expansion of urban communities and the expansion of industry and industrial life, the issue of environmental pollution and excessive increase in greenhouse gases has become one of the major problems of communities. Half of all carbon dioxide emissions are generated by fossil fuel and power plants. Synthesis gas, which includes carbon dioxide, carbon monoxide, hydrogen, methane, and nitrogen, is obtained by reforming natural gas. This gas is used to produce valuable products such as methanol. In general, methanol is produced from the hydrogenation of carbon dioxide and carbon monoxide separately in the presence of zinc oxide and copper catalysts by a complex mechanism. In this study, to increase methanol production in the unit, the effect of recycling different gas components in the industrial unit has been investigated using dynamic simulation. Also, the amount of carbon dioxide reduction and its effects on the environment are examined. These studies showed that by considering these changes, the rate of methanol production current can be increased by about two percent.

Research method of rapid determination of chiral pesticide fenpropathrin enantiomers in fruit and vegetable puree by supercritical fluid chromatography.

A method is first established for the separation and determination of fenpropathrin enantiomer residues in apple puree, strawberry puree, and tomato puree considered a supplementary food for infants by supercritical fluid chromatography. After the sample was extracted with acetonitrile and cleaned up by a solid-phase extraction column, then it was separated by a CHIRALPAK AD-3 chiral column with gradient elution at a flow rate of 1.5mL/min using methanol and supercritical carbon dioxide as the mobile phase, detected by ultraviolet detector at 230nm wavelength and quantified with the external standard method. The limits of quantification of the two fenpropathrin enantiomers were both 0.2mg/kg, the linear ranges were 1.0-20.0mg/L with linear correlation coefficients greater than 0.9992, the recoveries in the spiked samples at 0.2, 0.4 and 2.0mg/kg were from 80.6 to 105%, and the relative standard deviation reached 2.6-7.7%. This method has the advantages of convenient operation, good resolution, and environmental protection, which can satisfy the requirement of determination for fenpropathrin enantiomer residues in fruit and vegetable puree as supplementary food for infants.

Diffusion coefficients at infinite dilution of carbon dioxide and methane in water, ethanol, cyclohexane, toluene, methanol, and acetone: A PFG-NMR and MD simulation study

Diffusion coefficients at infinite dilution are important basic data for all processes involving mass transfer. They can be obtained from studying samples in equilibrium using nuclear magnetic resonance spectroscopy with pulsed field gradients (PFG-NMR), a technique which is widely used in chemistry but is only rarely applied in engineering studies. This advantageous technique was employed here to measure the self-diffusion coefficients of diluted solutions of carbon dioxide and methane in the pure solvents water, ethanol, cyclohexane, toluene, methanol, and acetone at 298.15 K. For the systems (carbon dioxide + water) and (carbon dioxide + ethanol), measurements were also carried out at 308.15 K, 318.15 K and 333.15 K. Except for (methane + water) and (methane + toluene), no literature data for the methane-containing systems were previously available. At the studied solute concentrations, there is practically no difference between the self-diffusion coefficient and the mutual diffusion coefficient. The experimental results are compared to experimental literature data as well as to results from semi-empirical methods for the prediction of diffusion coefficients at infinite dilution. Furthermore, molecular dynamics simulations were carried out for all systems to determine the diffusion coefficient at infinite dilution based on force fields that were taken from the literature, and the results are compared to the experimental data and those from the classical prediction methods.

Analytical research on the separation and residue of chiral pesticide triadimenol in fruit and vegetable puree.

In this paper, a method for the separation of triadimenol stereoisomers using ultra-performance convergence chromatography and an analytical method for the determination of triadimenol stereoisomer residues in pumpkin puree, apple puree, and tomato puree as a supplement for infants are established. Test samples were extracted with acetonitrile and successively purified with graphitized carbon black and Florisil column. Afterward, Acquity Trefoil AMY1 column was adopted for chiral separation of chromatographic column, and gradientelute was carried out with supercritical carbon dioxide-methanol as the mobile phase and with external standard method for quantitation. Results showed that the linearly dependent coefficient of the four kinds of triadimenol stereoisomers within 1.0 and 50mg/L was greater than 0.9997, and the limit of quantitation of the four kinds of triadimenol stereoisomers was 0.05mg/kg. Recovery experiment was carried out within 0.05 and 1.0mg/kg scope, the recoveries were 81.0-107％, and the relative standard deviation was 2.3-7.6%. This method implemented the separation of triadimenol stereoisomers and its residue test in pumpkin puree, apple puree, and tomato puree as a supplement for infants, and it can provide reliable technical support for the analysis of pesticide residue and assessment of product quality.

Design and thermodynamic analysis of a novel methanol, hydrogen, and power trigeneration system based on renewable energy and flue gas carbon dioxide

In this paper, a new trigeneration system is proposed to decrease atmospheric carbon dioxide emission and produce methanol, hydrogen, and power. The system is composed of an organic Rankine cycle, a direct methanol fuel cell, a carbon capture unit, a proton exchange membrane electrolyzer, and a methanol synthesis unit. A flue gas stream with a defined composition, solar energy, and the atmospheric air are the system's inlets. In the design step, special attention is paid to heat and mass integration between different components so that its waste can be lowered as much as possible. Then, mass balance law, energy conservation principle, exergy relations, and auxiliary equations are applied for each subsystem to investigate the system's thermodynamic performance. Also, the effect of changing operating parameters on the performance of each subsystem is studied. The obtained results show that the proposed system has the energy and exergy efficiencies of 66.84% and 55.10%, respectively. Furthermore, 94% of the total exergy destruction rate belongs to the water electrolyzer, while the contribution of the organic Rankine cycle is negligible. The performance of the methanol synthesis reactor depends strongly on its inlet temperature. Maximum equilibrium methanol concentration and carbon dioxide conversion are achieved at the inlet temperature of 210 °C. The parametric studies reveal that there is an optimum fuel cell current density in which its produced power density is maximized.

Modeling fluid phase equilibria of carbon dioxide-methanol binary system

Accurate fluid phase equilibria modeling of carbon dioxide-methanol binary system is essential for numerous industrial applications. Prior modeling studies were limited in scope in terms of temperature and pressure ranges. In this study, the phase equilibria behavior of the binary system is modeled with cubic equations-of-state (EoS) including Peng–Robinson (PR) and Soave–Redlich–Kwong with various mixing rules, Predictive Soave–Redlich–Kwong, Cubic Plus Association, and Perturbed-Chain Statistical Associating Fluid Theory. Among them, the classical PR EoS and its variants yield the overall best results in representing the phase behavior at temperature above 330 K. However, PR incorrectly predicts two liquid phases when the CO2 mole fraction exceeds ~ 0.4 at temperature lower than 330 K. Raoult's law with the classical nonrandom two-liquid excess Gibbs energy model is recommended for the low temperature conditions.

Nanosheet Synthesis of Mixed Co3O4/CuO via Combustion Method for Methanol Oxidation and Carbon Dioxide Reduction.

This paper represents a study of mixed Co3O4/CuO nanosheet (NS) synthesis via solution combustion synthesis for oxidation of methanol and carbon dioxide (CO2) conversion. The mixed oxide NS of Co3O4/CuO is a hybrid structure of Co3O4 and CuO NSs. We applied this mixed oxide NS of Co3O4/CuO for methanol oxidation and carbon dioxide (CO2) conversion, and the results revealed that the activity of the mixed oxide NS surpassed the activity of the corresponding individual Co3O4 and CuO metal oxide NSs, both in methanol oxidation and in CO2 conversion. The mass activity of the mixed Co3O4/CuO NS produced at 0.627 V versus Ag/AgCl during methanol oxidation (0.5 M) was 12 mA g-1, which is 2.4 times better than that of Co3O4, whose mass activity is 5 mA g-1, and 4 times better than that of the CuO NS, whose mass activity is 3 mA g-1. The methanol oxidation peak at 0.62 V versus Ag/AgCl was also more intense than individual oxides. The trend in performance of methanol oxidation follows the order: Co3O4/CuO > Co3O4 > CuO. In the case of CO2 reduction, we experienced that our product was formate, and this was proved by formate oxidation (formate is formed as a product during the reduction of CO2) on the surface of the Pt ring of a rotating ring-disc electrode. Similar to methanol oxidation, Co3O4/CuO also showed superior activity in carbon dioxide reduction. It was experienced that at -1.5 V, the current density rises to -24 mA/cm2 for the Co3O4/CuO NS, that is, 0.6 times that of the CuO NS, which is -15 mA/cm2, and 3 times more than that of the Co3O4 NS, which is 8 mA/cm2. The trend in performance of CO2 reduction follows the order: Co3O4/CuO > CuO > Co3O4.

Analysis of flavonoids with unified chromatography-electrospray ionization mass spectrometry-method development and application to compounds of pharmaceutical and cosmetic interest.

In this project, we aimed at analysing flavonoid-type compounds with unified chromatography (joining supercritical fluid chromatography and enhanced fluidity liquid chromatography with carbon dioxide-methanol mobile phases covering a wide range of compositions) and diode-array and electrospray ionization mass spectrometric detection (UC-DAD-ESI-MS). First, the chromatographic method was developed for 9 standard flavonoid molecules from three different families (flavanols, flavanones and flavonols, glycosylated or not), with a strong focus on mobile phase composition to achieve the elution of a wide range of flavonoids with good chromatographic quality (efficiency and resolution). For this purpose, two stationary phases were selected (ACQUITY UPC2 DEA and Diol), and five different additives (formic acid, citric acid, phosphoric acid, methanesulfonic acid and ammonium hydroxide) were successively introduced in the methanol co-solvent. The composition containing 0.1% methanesulfonic acid in methanol was retained as it provided the best chromatographic quality together with the possibility of hyphenating the chromatography to mass spectrometry. The DEA column appeared to provide the best efficiency and was retained for further method development. The gradient method was then optimized to achieve a fast analysis, which involved elution with a wide range of mobile phase composition (from 20 to 100% co-solvent in methanol) together with reversed flow rate and reversed pressure gradients at fixed temperature. The final gradient lasted 10min, followed by 2.5min of re-equilibration. Then, ESI-MS detection was optimized. Because the single-quadrupole mass spectrometer employed (ACQUITY UPC2 QDa) allowed the variation of only a few parameters, a design of experiments was used to define the best compromise for three parameters (probe temperature, cone voltage and capillary voltage). The make-up fluid introduced before entering the MS was also varied: different compositions of methanol-water containing either formic acid, ammonium hydroxide or sodium chloride were tested. The best results in terms of signal-to-noise ratio were obtained with methanol containing 20mM ammonium hydroxide and 2% water. The optimal UC-DAD-ESI-MS method was then applied to two different flavonoid formulation ingredients. The first one, hidrosmin (5-O-(β-hydroxyethyl)diosmin), is known for its vasoprotective properties and therefore employed in pharmaceutical formulations. The second one, α-glucosyl-hesperidin (sometimes referred to as vitamin P), is employed in cosmetic formulations. Identification of the major compounds in each sample was achieved with the help of MS detection. Graphical abstract.

Development of CuAg/Cu2O nanoparticles on carbon nitride surface for methanol oxidation and selective conversion of carbon dioxide into formate

Herein we report a catalyst consisting of CuAg/Cu2O nanoparticles (NPs), synthesized on the two-dimensional carbon nitride (CN) surface via galvanic exchange route for electrocatalytic methanol oxidation and carbon dioxide reduction. The lower reduction potential of copper ([Cu+(aq) + e− → Cu(s)], + 0.52 eV) compared to Ag ([Ag+(aq) + e− → Ag(s)], +0.80 eV) makes Cu(0) easily exchangeable by Ag+ ions via galvanic exchange without applying any external bias. In a two-step process, the Cu NPs are synthesized first on CN surface by adsorbing Cu2+ precursors and reducing them by NaBH4. Due to unstable nature of Cu2+ in aqueous medium some Cu2O NPs (a mixed phase of Cu/CuO) were also formed. Thereafter in the second step, Ag+ precursors are brought in contact with the already synthesized Cu and Cu2O nanoparticles (NPs). The Cu and Cu2O NPs present on the surface of CN are partially exchanged by Ag atoms to generate bimetallic CuAg/Cu2O NPs. Two atoms of Ag are expected to be deposited for every Cu atom replaced. As galvanic replacement occurs on the solid surface of carbon nitride, there is only a partial replacement of Cu and Cu2O atoms. The catalysts CN/Cu/Cu2O and CN/CuAg/Cu2O were evaluated for their performance towards methanol oxidation and carbon dioxide reduction. CN/CuAg/Cu2O showed twice the current density for methanol oxidation than CN/Cu/Cu2O in a 0.5 M methanol solution. Probably the reason for high activity of Ag than Cu is related to the weak bond of oxygen on silver substrate for oxidation reactions and strong binding affinity on copper substrate. In case of carbon dioxide reduction (CO2 reduction) the product was identified to be formate by oxidizing the product (formate) on a Pt ring electrode. The results revealed CN/CuAg/Cu2O shows a better selectivity towards formic acid formation than CN/Cu/Cu2O using the rotating ring disc electrode (RRDE). A probable reason may be the strain induced by alloy formation which could favor a reduced coverage of adsorbed hydrogen and a decrease in oxophilicity of the compressively strained copper.

Conversion and storage of solar energy in the forms of liquid fuel and electricity in a hybrid energy storage system using methanol and phase change materials

The utilization of solar-assisted hybrid energy systems is an appropriate way to generate green power. To this aim, an innovative hybrid charging/discharging system comprised of solar dish collectors, methanol synthesis unit, power cycles, and carbon dioxide liquefaction process as well as phase change materials, is introduced and thermodynamically assessed. An ammonia/water absorption refrigeration cycle is applied for the carbon dioxide liquefaction process. The proposed structure is simulated by using HYSYS, TRNSYS, and MATLAB, and a thermodynamics framework is conducted to assess the integrated system performance. The proposed structure successfully produces 8.449 kg/s and 11.49 kg/s of methanol liquid carbon dioxide, respectively. Energy analysis of this integrated system indicates that, the overall thermal efficiency of the charging and discharging modes are 0.8486 and 0.4076, respectively. The results of exergy evaluation reveal that the largest exergy destruction in the charging and discharging modes are related to collectors with 34.07% and reactors with 56.58%, respectively. In addition, the overall exergy efficiency of the charging and discharging cycles are 57.11% and 42.32%, respectively. A comparison between the proposed system and similar works show that the energy efficiencies of the power cycles are higher than similar studies. Finally, sensitivity analyses on the influence of various parameters such as useful energy collected by collectors, stored heat of phase change materials, solar collector thermal efficiency, irreversibility, and exergy efficiency in the cycle and collector are performed.

Electrocatalytic synthesis of organic carbonates.

Organic carbonates are considered environmentally benign alternatives for various fossil-derived compounds used in the chemical industry. Replacing current costly and toxic production methods by greener alternatives offers opportunities to cover the increasing demand for these intermediates in a more sustainable manner. In this feature article, the prospect of electrochemical synthesis of organic carbonates is presented as an approach to use carbon dioxide and green electricity to arrive at such compounds. We explore the strengths and limitations of the different methods by looking into the electrode and electrolyte composition effects and operating conditions with a focus on the synthesis of dimethylcarbonate from methanol and either carbon monoxide or carbon dioxide. The proposed mechanisms are discussed in an effort to understand the underlying steps and their challenges. This review concludes with a perspective on the broader developments needed to turn the basic chemistry into a practical application.

Electrochemical Carbon Dioxide Reduction in Methanol at Cu and Cu2O-Deposited Carbon Black Electrodes

The electrochemical reduction of carbon dioxide in methanol was investigated with Cu and Cu2O-supported carbon black (Vulcan XC-72) nanoparticle electrodes. Herein, Cu or a Cu2O-deposited carbon black catalyst has been synthesized by the reduction method for a Cu ion, and the drop-casting method was applied for the fabrication of a modified carbon black electrode. A catalyst ink solution was fabricated by dispersing the catalyst particles, and the catalyst ink was added onto the carbon plate. The pH of suspension was effective for controlling the Cu species for the metallic copper and the Cu2O species deposited on the carbon black. Without the deposition of Cu, only CO and methyl formate were produced in the electrochemical CO2 reduction, and the production of hydrocarbons could be scarcely observed. In contrast, hydrocarbons were formed by using Cu or Cu2O-deposited carbon black electrodes. The maximum Faraday efficiency of hydrocarbons was 40.3% (26.9% of methane and 13.4% of ethylene) at −1.9 V on the Cu2O-deposited carbon black catalyst. On the contrary, hydrogen evolution could be depressed to 34.7% under the condition.

Solvation of Hydroxybenzoic and Hydroxycinnamic Acids in Supercritical Carbon Dioxide: Formation of Hydrogen Bonds with a Polar Cosolvent

Selective solvation of ortho-hydroxybenzoic, meta-hydroxybenzoic, para-hydroxybenzoic, protocatechal, gallic, lilac, para-coumaric, and caffeic acids with a polar cosolvent (methanol) in supercritical carbon dioxide was studied at 318 K at a density of 0.7 g/cm3 and a methanol concentration of 3.5 mol % with conventional molecular dynamics. We studied the localization of a cosolvent in the nearest environment of a solute, the formation of cosolvent clusters around the solute, and the number and nature of hydrogen bonds between molecules of the solute and cosolvent. We also considered the structural features of hydrogen-bound complexes associated with a molecular structure of a solute (the number and the arrangement of hydroxyl groups, the substitution of hydroxyl hydrogen atoms with methyl moieties, and the presence of an ethylene group).

Characterization of Novel Polymer-Based Pyridine Stationary Phases for Supercritical Fluid Chromatography

2-Ethylpyridine-bonded silica is one of the most famous stationary phases employed in supercritical fluid chromatography, especially for the analysis of basic compounds and even without an additive in the mobile phase. In the present paper, we present the synthesis and characterization of three original stationary phases based on poly(vinylpyridine) polymers supported on silica. The position of nitrogen atom relative to the polymer chain was varied to be in the 2, 3, or 4 position. All these phases were prototypes, while the poly(4-vinylpyridine) phase was subsequently commercialized (DCPak P4VP from Daicel Corporation). The stationary phases obtained are characterized in supercritical fluid chromatography with carbon dioxide—methanol mobile phase, with a modified version of the solvation parameter model, to take account of ionic interactions. The three phases are also compared to a 2-ethylpyridine-bonded silica phase and a 2-picolylamine-bonded silica phase. It appears that the polymer-based pyridine phases are significantly more retentive than brush-type pyridine phases and adequately shield residual silanol groups to prevent unwanted interactions with basic compounds. The different selectivities and chromatographic performances are also evidenced with sample applications on pharmaceutical compounds, notably with a selection of 140 drug candidates.