Determination of crystal growth rate for porcine insulin crystallization with CO2 as a volatile acidifying agent

Crystallization is controlled by two steps that determine the quality and the final size of the product, nucleation and growth, which are functions of supersaturation. Recently, Hirata et al. [1] crystallized insulin using CO₂ as a volatile acid to impose supersaturation on the system. The objective of the present work was to determine the growth kinetics of insulin crystallization in 50 mM NaHCO₃ solution with 0.4 mM ZnCl₂ in a CO₂ atmosphere at 15 °C, adjusting the parameters of the equation G = k_g × S^g to the experimental data. The solubility of insulin in the NaHCO₃/CO₂/ZnCl₂ system at 15 °C was determined as a function of pH in the range of 6.30–7.34. The crystal growth data allowed determination of the growth order “g” (g = 2.9). Although protein crystallization has some features that differ from the crystallization of less complex molecules, the apparent growth kinetics of insulin were successfully analyzed here with the same empirical methods used for small molecules, which can easily be scaled up for industrial applications to achieve specific size and purity, the goals of industrial crystallization. The method used in this work is a useful tool for describing and simplifying optimization of industrial protein crystallization processes.     

Crystallization of acetaminophen micro-particle using supercritical carbon dioxide

Fine particles of acetaminophen were produced by Aerosol Solvent Extraction System (ASES). The experiments were conducted to investigate the effects of various temperatures, pressures, solvents, solution concentrations and solution feed volume rates on particle size and morphology. The choice of solvent appears to be very important for getting specific particle shape and size. The result shows that when ethyl acetate is used as a solvent, the irregular and acicular morphology of raw material is recrystallized to be regular and monoclinic. The average particle size of recrystallized acetaminophen from ethyl acetate solution has been measured to be 3–4 Μm, which was about 1/20th of raw acetaminophen in size. The particle size distribution range also became narrow from 82 Μm to 4.9 Μm.     

Crystallization characteristics of polyoxymethylene with attapulgite as nucleating agent

The nucleation of polyoxymethylene (POM) crystallization using attapulgite was studied using differential scanning calorimetry, polarized light microscopy, wideangle X‐ray diffration and mechanical testing. Two isothermal crystallization kinetic equations were employed to describe the crystallization of virgin POM and POM containing attapulgite as a nucleating agent. The addition of attapulgite decreased the spherulitic size of POM, and interfacial free energies per unit area perpendicular to the molecular chain direction ρ_e, accelerated the crystallization growth rate and enhanced the impact toughness of POM, but no change occurred for the hexagonal system of POM. The addition of attapulgite up to its saturation concentration in POM increased the number of effective nuclei by three orders of magnitude. A high concentration of attapulgite caused agglomeration of the agent and lowered the number of effective nuclei.     

Kinetic study of Argentinean asphaltite gasification using carbon dioxide as gasifying agent

The kinetics of Argentinean asphaltite char gasification using carbon dioxide as gasifying agent was studied between 1048 and 1223 K. The chars were obtained by pyrolysis of an asphaltite in a fixed bed reactor. The relative mass change during the gasification reaction was continuously monitored using a high resolution thermogravimetric system. The starting temperature for the reaction of the char with carbon dioxide was determined at about 800 K. The influence of gaseous flow rate, sample mass, carbon dioxide partial pressure and temperature in the reaction rate was analyzed. The experimental condition under which the progress of gasification reaction is chemically controlled was established. In those conditions, an activation energy of 185 kJ mol⁻¹ was obtained with an isoconversional method. Concerning the influence of carbon dioxide partial pressure, it was determined that pressures greater than 50 kPa do not alter the kinetics regime. Finally a reaction order of 0.5 for carbon dioxide partial pressure was determined and a global rate equation that includes these parameters was developed.

     

Layered-silicate based polystyrene nanocomposite microcellular foam using supercritical carbon dioxide as blowing agent

Exfoliated layered-silicate in the polystyrene (PS) block copolymer with different molecular weights was employed as a model material to investigate the PS nanocomposite microcellular foams expanded by supercritical carbon dioxide. Using a well-controlled foaming procedure, we investigated the influence of molecular weight of PS, dispersion and loading of layered-silicate and pressure drop rate of a blowing agent on the cell size and cell density. Our experimental results indicate that only exfoliated layered-silicate can inhibit the cell expansion and has high nucleation efficiency during foaming. The average cell diameter can be reduced from 6 μm to 1.4 μm and the cell density can be increased from 7.6 × 10⁹ cells/cm³ to 5.0 × 10¹¹ cells/cm³. On the contrary, aggregated layered-silicate in PS did not show any effect on the cell morphology of PS foam.     

Mesoporous silica particles grafted with polystyrene brushes as a nucleation agent for polystyrene supercritical carbon dioxide foaming

In this study, spherical ordered mesoporous silica (s‐OMS) was applied as a new type of nucleating agent in polystyrene (PS) foaming with supercritical CO₂ as a blowing agent. These s‐OMS particles were modified by the selective grafting of PS brushes on the outside surface, by which the mesoporous structure inside particles could be maintained. Transmission electron microscopy, X‐ray diffraction, thermogravimetric analysis, Fourier transform infrared spectroscopy, and Brunauer–Emmett–Teller surface area analysis were used to characterize the structure of the original and modified particles; these indicated that the PS brushes were grafted on the outside surface and the inside porous structure were maintained. PS/s‐OMS–PS composites were prepared by a solution blending method, and the s‐OMS–PS particles could have been well dispersed in the PS matrix because of the surface modification. Subsequently, PS and composite microcellular foams were prepared by a batch foaming process, and the morphology characterization on these foams showed that the s‐OMS particles exhibited an excellent heterogeneous effect on PS foaming. The heterogeneous effect became more significant when the foaming temperature or saturation pressure was low. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4308–4317, 2013     

Sulfur dioxide as an activating agent for sulfur-impregnated activated carbon produced from dense petroleum coke

To develop novel sorbent materials for capturing vapor mercury from industrial flue gases at high temperatures, high-sulfur oil-sands fluid coke was activated using 50% sulfur dioxide (SO₂) at 700°C under various pre-treatment conditions. Pyrolysis in nitrogen prior to activation significantly decreased specific surface area (SSA) of the product, which was attributed to the thermoplastic behavior of coke at high temperatures. Air pre-oxidation suppressed this effect and provided an enhancement over non-pyrolyzed coke, with SSA peaking at 447 m²/g after 5 h activation. Acid washing of air pre-oxidized activated coke in 10% hydrochloric acid increased SSA by removal of inorganic ash which added weight but contributed minimal surface area. Decreasing initial particle size range from 212–300 to 53–106 μm significantly increased SSA, which was attributable to an outer porous layer of constant thickness. Under optimized conditions, an SSA of 531 m²/g was achieved – the highest reported in literature for physically activated fluid coke. Coke activated with SO₂ displays a high mesoporous fraction and pore surface coverage by sulfur groups that were thermally stable up to 500°C.     

Challenge to fortyfold expansion of biodegradable polyester foams by using carbon dioxide as a blowing agent

This paper presents a new foaming technology using supercritical carbon dioxide as a blowing agent to obtain large volume expansions of biodegradable polyester foams of over fortyfold. The basic approach for the promotion of a large volume expansion ratio with carbon dioxide was to prevent cell coalescence by using a branched material, to dissolve carbon dioxide completely in the melt by promoting convective diffusion under a high processing pressure, to reduce the diffusivity of gas by lowering the melt temperature, and to optimize the processing conditions in the die to maximize volume expansion. The desirable composition of the materials includes dehydrated branched biodegradable polyester (polybutylene succinate), CO₂ (blowing agent), and tale (nucleating agent). A single‐screw extrusion system was used for foam processing. A large volume expansion ratio of up to forty‐fivefold was achieved from the biodegradable polyester foams. The morphologies and volume expansion ratios of biodegradable polyester foams at various processing temperatures and pressures were studied.     

Introducing water as a coblowing agent in the carbon dioxide extrusion foaming process for polystyrene thermal insulation foams

In this study, water was used as a coblowing agent in the carbon dioxide (CO₂) extrusion foaming process in a twin screw extruder. It enlarged cell size and thus lowered foam density for better thermal insulation. Different strategies have been studied including direct injection of water into the extruder with surfactants, extrusion foaming of water expandable polystyrene (WEPS) beads, and feeding water containing activated carbon (WCAC)/polystyrene (PS) pellets. It was found that WCAC/PS pellets provided the most stable and clean extrusion process, more uniform cell morphology, and better thermal insulation than other methods. POLYM. ENG. SCI., 50:1577–1584, 2010. © 2010 Society of Plastics Engineers     

Catalytic reduction of carbon dioxide. 1. Reduction of carbon dioxide with carbon carrying potassium carbonate

The catalytic behaviour of potassium carbonate doped onto active carbon was investigated with respect to reduction of carbon dioxide. The distribution of potassium on the carbon surface was found by an X-ray microanalyzer to be uniform. The amount of oxygen trapped on the carbon surface during reaction was nearly proportional to the surface concentration of potassium. The catalytic activity with carbon doped with less than 2% potassium carbonate was proportional to the amount of trapped oxygen, while excessive doping by potassium was found to form trapped oxygen independently of the gasification of carbon. Disproportionation of carbon monoxide into carbon dioxide and carbon was found to take place readily at 700 °C, with carbon doped with 4.0 wt % potassium carbonate.     

离子液体作为CO_2吸附剂的研究进展

离子液体(ILs)是完全由特定阳、阴离子构成的在室温或近于室温下呈液态的物质,是一类新型"软"功能材料或介质,CO2能与ILs发生强相互作用,在其中具有很高的溶解度。本文综述了CO2在传统离子液体、功能化离子液体、聚合离子液体及其他形式离子液体中的溶解度,讨论了CO2在离子液体中溶解度的影响因素以及计算机模拟在离子液体溶解CO2研究中的应用,指出了离子液体作为吸收剂的优缺点,展望了其代替传统CO2吸收剂的研究前景。     

Melt foamability of reactive extrusion‐modified poly(ethylene terephthalate) with pyromellitic dianhydride using supercritical carbon dioxide as blowing agent

By reactive extrusion with pyromellitic dianhydride (PMDA), foamable poly(ethylene terephthalate) (PET) was obtained, which achieved a maximum intrinsic viscosity of 1.36 dL/g with PMDA content 0.8 wt%. Dynamic shear rheological properties were measured to characterize the structure evolution of modified PET. And the Avrami analysis was extended for the non‐isothermal crystallization process of modified PET, which relates to cell stabilization in the melt foaming process. Based on the batch foaming process with supercritical carbon dioxide as blowing agent, broad foaming temperature windows were obtained for PETs modified with 0.8 and 0.5 wt% PMDA, in which PET foams with the expansion ratio between 10 and 50 times, the cell diameter between 15 and 37 μm, and the cell density between 6.2 × 10⁸ and 1.6 × 10⁹ cells/cm³ were controllably produced. POLYM. ENG. SCI., 55:1528–1535, 2015. © 2014 Society of Plastics Engineers     

A parametric study into the morphology of polystyrene-co-methyl methacrylate foams using supercritical carbon dioxide as a blowing agent

In this study the foaming of poly(styrene-co-methyl methacrylate) (SMMA) using supercritical carbon dioxide is investigated. The effect of different foaming parameters such as temperature and pressure is studied in a quantitative and systematic way, with the aim to control and predict the resulting foam morphology. It is shown that once the polymer properties, such as the glass transition temperature and the solubility of CO₂ are known, full control of the desired foam morphology can be obtained by a proper selection of temperature, pressure and depressurization rate.     

Crystallization of poly(lactic acid) enhanced by phthalhydrazide as nucleating agent

The effect of phthalhydrazide compound on the nonisothermal and isothermal crystallization behavior of bio-based and biodegradable poly(lactic acid) (PLA) was investigated by differential scanning calorimetry and polarized optical microscopy. The nonisothermal melt crystallization of PLA started much earlier in the presence of phthalhydrazide even at a phthalhydrazide content as low as 0.1 wt%. The isothermal crystallization kinetics was analyzed by the Avrami model. It was found that the Avrami exponent of the PLA crystallization was not significantly influenced by the addition of phthalhydrazide, indicating that the crystallization mechanism almost did not change in the composites. The crystallization half-time of PLA/phthalhydrazide composites decreased significantly with increase in phthalhydrazide loading. The observation from optical microscopy showed that the presence of phthalhydrazide increased the number of nucleation sites. The above observations indicate that phthalhydrazide is an efficient nucleating agent of PLA.     

Solubility of chemical warfare agent simulants in supercritical carbon dioxide: experiments and modeling

Solubility data are reported for ethyl phenyl sulfide (EPS) and 2-chloroethyl ethyl sulfide (CEES) in CO₂ at temperatures from 25 to 100 °C. These two sulfide-based compounds are homomorphs for chemical warfare agents (CWAs). Both sulfide–CO₂ mixtures exhibit type-I phase behavior. The maximum in the 100 °C isotherm is approximately 2600 psia for the CEES–CO₂ system and approximately 3400 psia for the EPS–CO₂ system. The Peng–Robinson equation of state (PREOS) is used to model both sulfide–CO₂ mixtures as well as the phase behavior of the 2-chloroethyl methyl sulfide (CEMS)–CO₂ system previously reported in the literature. The Joback–Lydersen group contribution method is used to estimate the critical temperature, critical pressure, and acentric factor for the sulfides. Semi-quantitative estimates of the phase behavior are obtained for the CEES–CO₂ and EPS–CO₂ systems with a constant value of k_ij, the binary interaction parameter, fit to the 75 °C isotherms. However, very poor fits are obtained for the 2-chloroethyl methyl sulfide–CO₂ system regardless of the value of k_ij. On the basis of the high solubility of EPS and CEES in CO₂, supercritical fluid (SCF)-based technology could be used to recycle or recover chemical warfare materials.     

超临界CO2清洗技术

介绍了超临界CO2清洗的工艺及其应用,分析了超临界CO2清洗在技术、经济及环保方面的特点。     

Crystallization of poly(3‐hydroxybutyrate) with stereocomplexed polylactide as biodegradable nucleation agent

Crystallization kinetics behavior and morphology of poly(3‐hydroxybutyrate) (PHB) blended with of 2–10 wt% loadings of poly(L ‐ and D ‐lactic acid) (PLLA and PDLA) stereocomplex crystallites, as biodegradable nucleating agents, were studied using differential scanning calorimetry, polarizing‐light optical microscopy (POM), and wide‐angle X‐ray diffraction (WAXD). Blending PLLA with PDLA at 1:1 weight ratio led to formation of stereocomplexed PLA (sc‐PLA), which was incorporated as small crystalline nuclei into PHB for investigating melt‐crystallization kinetics. The Avrami equation was used to analyze the isothermal crystallization of PHB. The stereocomplexed crystallites acted as nucleation sites in blends and accelerated the crystallization rates of PHB by increasing the crystallization rate constant k and decreasing the half‐time (t_1/2). The PHB crystallization was nucleated most effectively with 10 wt% stereocomplexed crystallites, as evidenced byPOM results. The sc‐PLA complexes (nucleated PHB crystals) exhibit much small spherulite sizes but possess the same crystal cell morphology as that of neat PHB based on the WAXD result. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers