Supercritical CO2 Spray Drying of Ethyl Cellulose (EC) for Preparing Microparticles

Even though common spray drying has been widely used for drying food and related products, the effect of drying conditions of supercritical CO₂ spray drying on the particle sizes of dried products has not been well studied. The objective of this study was to study the effect of drying conditions and design parameters on the particle sizes of biomaterials dried with supercritical CO₂ spray drying. The ethyl cellulose (EC) microparticles were prepared with supercritical CO₂ as the dry medium using an experimental spray-drying apparatus. This research studied the influences of spray nozzle diameter, mass ratio of gas to liquid, solution concentration, temperature, and pressure on the physical characteristics of ethyl cellulose microparticles. The results indicated that the average size of the dried particles ranged from 1.07 to 9.84 µm. The spray nozzle with 8-mm diameter produced smaller microparticles with narrower distribution than the 4-mm spray nozzle. The average particle size increased with the increase of the ratio of gas to liquid. Also, the average size and distribution of the microparticles increased with the rise of temperature and solution concentration but decreased with the increase of pressure.     

纳米锑掺杂氧化锡制备中超临界CO_2干燥的工艺优化及动力学

纳米锑掺杂氧化锡(ATO)具有优越的光电性能,在制备过程中前驱体干燥处理至关重要。为掌握ATO前驱体的超临界CO2干燥工艺特性,研究了超临界干燥的时间、温度、压力和CO2流量等工艺参数对纳米ATO粒径、比表面积等的影响,进一步探讨了超临界CO2流量对干燥动力学的影响规律,并拟合了干燥曲线方程。结果表明:温度35~40℃、压力10~14 MPa、CO2流量1.2~1.8 L·h-1、干燥5~6 h,最终能够获得平均粒径20~30 nm、高比表面积的纳米ATO材料;流量对干燥速率有明显影响,醇分比0.4为干燥速率由恒速转为降速的临界点,醇凝胶干燥动力学方程能够很好地描述ATO醇凝胶干燥工艺过程。研究结果可为湿法制备纳米材料的湿凝胶干燥工业化生产和控制提供参考。     

Spray drying conditions and encapsulating composition effects on formation and properties of sodium diclofenac microparticles

This paper reports the preparation and characterization of sustained release sodium diclofenac microparticles by spray drying. Aqueous dispersions of ethyl cellulose (Surelease®) and Eudragit RS 30 D® were evaluated as controlled release polymers. The product properties (product moisture, size distribution, particle morphology, flow properties, total drug load, in-vitro dissolution studies, and encapsulating efficiency) were determined as a function of inlet temperature of the spray drying, the feed flow rate and composition of the microencapsulating formulation. In general, lower values of the product moisture content were observed at higher drying temperatures. The spray-dried product was composed mainly by rounded-shape and multi-size particles. The mean particle diameters of the Eudragit based microparticles tended to be slight bigger than the Surelease based microparticles. The spray dried microparticles showed delayed drug dissolution rates, sustaining the drug release for several hours. These findings confirm the feasibility of the spray drying for preparation of microparticles with sustained release properties. The physical and chemical properties of the microparticles can be changed by varying the spray drying parameters as well as the microencapsulating formulation.     

Prediction of the viscosity reduction due to dissolved CO2 of and an elementary approach in the supercritical CO2 assisted continuous particle production of a polyester resin

The dissolution of CO₂ in a polymer causes plasticization of the polymer and hence, its viscosity is reduced. A model based on the free volume theory has been used for a polyester resin, which shows a considerable reduction in the viscosity due to dissolved CO₂. Therefore, supercritical CO₂ has been used as a processing solvent in the continuous production of micron size particles of the resin. Despite the viscosity reduction caused by the dissolved CO₂, an excess quantity of CO₂ with respect to its solubility limit has been used for micronisation of the polymer due to its high viscosity. The mixing of CO₂ and the polymer has not been possible in an extruder at high gas to polymer mass ratios and consequently, a simplified Kenics type static mixer has been used for the mixing purpose. In this study, the effect of various parameters such as temperature, pressure, nozzle diameter and gas to polymer mass ratio on the particle morphology and size has been studied. The experimental results manifest the technological as well as the theoretical insight into the particles production from a high viscosity material.     

SELECTIVE GAS ABSORPTION UNDER PRESSURE

For selective removal of H2S from much larger quantities of CO₂ under pressure, an industrial prototype spray column has been constructed. Sodium hydroxide solution was atomized by a pressure nozzle of special design and entered the scrubber as fine spray to contact the sour gases.

Several operating variables were examined in order to indicate optimal operating conditions for maximum selectivity of H₂S over CO₂. Fine mist and short contact time favor this selective absorption process. An optimum inlet reactant concentration was found dependent upon the H₂S content relative to CO₂ in the inlet sour gas mixture. A special nozzle/shield configuration to avoid contact of sour gas with highly turbulent liquid during droplet formation significantly improved the selectivity.     

小尺度超临界CO2管道小孔泄漏减压及温降特性

超临界CO₂管道运行过程中一旦发生泄漏，将会造成严重的事故。本文基于小尺度CO₂管道（长14.85m，内径15mm）实验装置开展了超临界纯CO₂及含杂质超临界CO₂管道的小孔泄漏实验，测量了不同泄漏孔径及不同起始压力条件下超临界CO₂管道泄漏过程中管内介质的压力和温度响应曲线，分析了管道泄漏过程中CO₂的相态变化。研究结果表明，在超临界CO₂管道泄漏过程中，管内流体温度存在一个最低值，CO₂由超临界态直接转变为气态；泄漏孔径越大，管道泄漏时间越短，管内介质温度所能达到的最低值更低；N₂的存在缩短了管道泄漏的时间，提高了管内介质的最低温度，且N₂含量越高，该最低温度越高。此外基于管道泄漏时间的自保持性，得出了不同泄漏孔径和起始压力条件下管内压力随泄漏时间变化的经验公式。     

Supercritical CO2 precipitation of poly(l-lactic acid) in a wide range of miscibility

Polymer microparticles are useful for numerous applications such as stationary phases in chromatography, adsorbents and catalyst supports, as well as for drug delivery systems. In recent decades the application of supercritical fluids for microparticle precipitation has been developed to a point where it is an ideal alternative to conventional processes. In this work poly(l-lactic acid) (PLLA), a biodegradable and biocompatible thermoplastic aliphatic polyester, has been processed using supercritical fluids, particularly by rapid expansion of supercritical solutions (RESS) and supercritical antisolvent (SAS) processes over a wide miscibility range. Particle morphology was greatly improved from irregular blocks to spherical microparticles on applying the SAS process. The effects of changes in polymer concentration, liquid flow rate, nozzle diameter, solvent, pressure and temperature have also been evaluated on the particle size of PLLA in the SAS precipitation. A higher concentration of the initial solution led to a decrease in particle size. Dichloromethane was the best of the chlorinated solvents investigated. The nozzle diameter had a negligible effect on particle size and the highest liquid flow rate gave the largest particle size. A larger particle size was also obtained on increasing the operating temperature. In contrast, the particle size decreased on increasing the operating pressure.     

干燥温度对FeAl基催化剂结构与性能的影响

对共沉淀法制备的Fe Al基沉淀分别在不同温度下进行干燥,各样品经500℃焙烧后,再浸渍Zn、K和Cu助剂制备成催化剂,研究干燥温度对催化剂结构和性质的影响,并与催化剂的CO2加氢反应性能相关联,进行催化剂表征。XRD分析表明,干燥沉淀中的Fe存在状态依赖于干燥温度,80℃干燥样品中的Fe以无定形存在,140℃处理后的α-Fe OOH衍射峰最强,160℃时,α-Fe OOH开始脱水转化,180℃干燥产生α-Fe2O3晶体。α-Fe OOH在焙烧过程中转变成α-Fe2O3,但晶粒大小和助剂的分散度表现出对干燥温度的依赖。随着干燥温度的升高,相应催化剂的CO2加氢反应活性先增加再降低,140℃干燥的催化剂具有最高的反应活性。     

Performance of CO2 absorption in a diameter-varying spray tower

The application of spray towers for CO₂ capture is a development trend in recent years. However, most of the previous jobs were conducted in a cylindrical tower by using a single spray nozzle, whose configuration and performance is not good enough for industrial application. To solve this problem, the present work proposed a diameter-varying spray tower and a new spray mode of dual-nozzle opposed impinging spray to enhance the heat and mass transfer of CO₂ absorption process. Experiments were performed to investigate the mass transfer performance (in terms of the CO₂ removal rate (η) and the overall mass transfer coefficient (K_Ga_e2 are major factors, which affect the absorption performance and the maximums of η and K_Ga_e that are 94.0% and 0.574 kmol·m^-3·h^-1·kPa^-1, respectively, under the experimental conditions. Furthermore, new correlations to predict the mass transfer coefficient of the proposed spray tower are developed in various CO₂ concentrations with a Pearson Correlation Coefficient over 90%.     

Co-precipitation of amoxicillin and ethyl cellulose microparticles by supercritical antisolvent process

Microparticles of ethyl cellulose (EC) and amoxicillin (AMC) have been precipitated by a supercritical antisolvent process (SAS) using CO₂ as the antisolvent and a mixture of dichloromethane (DCM) and dimethyl sulfoxide (DMSO) as solvents. Combinations of three temperatures (308, 323 and 333 K) and four pressures (100, 150, 200 and 250 bar) were assessed in the vessel and the rest of the variables were held constant (i.e. CO₂ flow rate, sample flow rate, washing time, nozzle diameter and the amoxicillin:ethyl cellulose ratio). Scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and elemental analysis (EA) were used to determine the particle size and shape and to confirm the presence of both compounds in the resulting precipitates. In most cases, mixed amoxicillin and ethyl cellulose particles were produced with sizes in the micrometer range. Pressure and temperature effects on the co-precipitation were investigated. The release behaviour of the microparticles precipitated by the SAS process was evaluated in two biological fluids – simulated gastric and simulated intestinal fluids. Co-precipitated materials allowed a slower drug release rate than pure drug.     

Influence of Particle Size on the Drying Kinetics of Single Droplets Containing Mixtures of Nanoparticles and Microparticles: Modeling and Pilot-Scale Validation

The particle size of the primary particles is an important parameter influencing the drying behavior of droplets. In this work, the influence of particle size on the drying kinetics and grain properties was analyzed for droplets containing silica nanoparticles, microparticles, and mixtures of the two. The presence of microparticles was found to increase the drying rate and shrinkage of the droplet. The drying curves were modeled using a reaction engineering approach (REA) model. Finally, different suspensions were dried in a pilot-scale spray dryer in order to prove the influence of the particle size obtained in the levitator tests.     

Fabrication of composite microparticles of artemisinin for dissolution enhancement

The main aim of this study is to enhance the dissolution of a poorly water soluble antimalarial drug, artemisinin (ART) by fabricating its microparticles and composites with selected hydrophilic polymers using a spray drier with a modified multi-fluid nozzle. We investigated the spray drying of ART with polyvinylpyrrolidone (PVP) considering the effect of feed ratio (ART:PVP) on the physical properties and dissolution of spray dried ART. Other hydrophilic carriers such as polyethylene glycol (PEG) were selected for comparing the dissolution with that of spray dried ART with PVP. The drug and polymer solutions were supplied through different liquid passages of the modified four-fluid nozzle to fabricate ART and composite microparticles. Characterization of the original ART powder, spray dried ART microparticles and ART-polymer composite microparticles was carried out by scanning electron microscopy (SEM), Fourier transform infrared (FTIR), differential scanning calorimetry (DSC), X-ray diffraction (XRD) and dissolution tester. The DSC and XRD studies suggested that the crystallinity of ART decreased after spray drying and depended on the weight ratio of drug to polymer. Percent dissolution efficiency (%DE); relative dissolution (RD); mean dissolution time (MDT); difference factor (f₁) and similarity factor (f₂) were calculated for the statistical analysis. The dissolution of ART from the spray dried ART-PVP composite microparticles was more rapid than that from their respective physical mixture, spray dried ART-PEG composite microparticles and original ART powder. In the mathematical modeling, the Weibull and Korsmeyer-Peppas model were found to best fit to the in vitro dissolution data and the drug release kinetics could be recognized as Fickian diffusion. This study demonstrated that the modified multi-fluid spray drier can be used for the preparation of drug microparticles to improve the dissolution ability of poorly water soluble drugs and overcome the problem of finding a common solvent for drugs and carriers.     

Preparation of freestanding and crack-free titania–silica aerogels and their performance for gas phase, photocatalytic oxidation of VOCs

Freestanding and crack-free titania–silica aerogels with high titanium content (i.e., Ti/Si = 1) were successfully prepared by adjusting the hydrolysis of the two alkoxide precursors to a comparable rate during the sol–gel processing. Two titania–silica aerogels were prepared by ethanol and CO₂ supercritical drying methods. Well-dispersed, nanometer-sized anatase crystal domains (ca. 10 nm) were crystallized by high temperature, ethanol supercritical drying. The crystalline domains were solidly anchored to the aerogel network by Ti–O–Si bonds. Titania–silica aerogels prepared by CO₂ supercritical drying method were devoid of TiO₂ crystals. A molecular-level mixing was achieved and anatase TiO₂ was only crystallized with difficulty by high temperature calcination (1073 K). Both aerogels were mesoporous and displayed similar open pore structure that is readily accessible to reactant molecules. However, only the titania–silica aerogel with anatase TiO₂ prepared by ethanol supercritical drying was active for the gas phase, photocatalytic oxidation of volatile organic compounds (i.e., isopropanol and trichloroethylene). Catalysts prepared from Degussa P25 TiO₂ displayed lower activity under similar reaction conditions.     

压力雾化喷嘴在受限空间气流中喷雾特性的实验研究

对出口直径为0.21、0.28、0.38、0.46mm的4种压力雾化喷嘴及其组合在150mm×150mm×1 000mm的矩形通道中的喷雾流场进行了实验研究,矩形通道中的空气流速为10m/s。研究了喷嘴布置和组合方式对雾化流场的影响。实验结果表明:喷雾不碰壁距离随入射角的增大而增大;顺流喷雾比无气流时液滴的平均D32减小10%,粒径范围略有扩大;逆流喷雾比无气流时液滴的平均D32增大约70μm,粒径范围扩大了3⁴倍;出口直径小的喷嘴可通过逆流布置和顺流布置的组合,获得液滴粒径分布范围更宽的气液两相流场。双喷嘴在有限空间内的雾化效果与流场中气液流量比有关。所得研究结论对天然气加湿技术的开发有一定参考价值。     

LEAFLASH SPRAY DRYER: INVESTIGATION OF THE ATOMIZATION PROCESS

The atomization process of the LEAFLASH spray dryer has been investigated by laser diffractometry and video imaging. The LEAFLASH atomizer is a particular pneumatic nozzle where the pressurized gas is the hot drying air. The drying and the atomization processes are interrelated in the spray dryer. Consequently the mixing of the liquid droplets and the drying medium is very efficient, permitting to work with short drying duration and reduced chamber volume. The mean diameter and the drop size distribution are measured at the outlet of the nozzle by laser diffraction. We studied the coupling effects of the air temperature (150 to 300° C) and pressure (1.20 to 1.50 bars abs) and of the dry matter content of the liquid feed (aqueous maltodextrin solution, 20 to 55% w/ w) on the droplets/ size distribution and on the general pattern of the spray. Analyses of video images of the generated spray give the general pattern of the spray and an estimation of the liquid velocity     

Diffusion During the Supercritical Drying of Silica Gels

Drying is the most critical elaboration step of large monolithic and crack-free silica aerogel plates. In the present work, we are studying the supercritical CO₂ drying and more precisely the first step, here called the supercritical washing step. This phase consists of replacing the liquid phase contained in the nanopores with supercritical CO₂. Within this study, this step is governed by molecular diffusion through the gels. These phenomena were investigated experimentally in order to estimate the duration of the washing step. The experimental results were then fitted with an analytical mass transfer model to identify the effective diffusion coefficient.     

工业规模CO2管道泄放过程中的压力响应及相态变化

基于CO₂相态分别进行了气相、气液两相和超临界状态的3组工业规模CO₂管道(长256 m,内径233 mm)泄放实验,分析了CO₂管道泄放过程中的压力响应和相态转变过程。研究表明:在管道内,气相CO₂泄放开始时压力发生突降,而后压降停滞或减慢;管内相态主要为气态,但管道末端温度大幅下降使该处形成气液均相CO₂。泄放口位于气液界面之上的气液两相CO₂泄放中,减压波多次反射并导致多次压力突降和反弹;管内相态由气液分层向气液均相转变,管道顶部和底部气液均相CO₂先后向气相CO₂转变。超临界CO₂泄放中的压力突降和反弹发生在临界区域附近,且压力穿过临界压力时,压变速率会停滞或减慢;管内相态经历了超临界、气液均相和气相泄放3个过程。     

Solid-liquid separation in suspension atomization

The aim of this paper is to define the conditions controlling the fragmentation process within the atomization of a suspension. Correlations for the droplet diameter of a suspension spray generated by a twin-fluid nozzle have been derived. Two separate regimes in suspension atomization have been identified with respect to the solid particle size. The atomized droplets from suspensions containing relatively fine solid particles are suspension droplets (containing liquid and solid particles). In this case a correlation for the drop size distribution in the spray of a twin-fluid nozzle has been deduced. Droplet size measurements in the suspension spray with varying solid particle sizes showed that when the suspended solid particle size exceeds a critical value, solid particles and liquid will be more and more separated. This effect is indicated by a bimodal size distribution in the suspension spray. It is shown that complete solid-liquid separation in the suspension spray may be achieved, where the pure liquid drops are significantly smaller than the separated solid particles. The critical process conditions where the solid-liquid separation process is found will be derived. Depending on the operating conditions of the atomizer, the resulting pure liquid droplet size is equal or less than the hydraulic diameter.     

Use of Computational Fluid Dynamics to Evaluate Alternative Spray Dryer Chamber Configurations

A computational fluid dynamic simulation study was carried out to compare the gas flow and temperature patterns as well as particle trajectories for a pressure nozzle atomized liquid slurry spray dried in four different chamber geometries. The gas and liquid conditions are held the same for all four chamber geometries. The gas flow is co-current and enters and exits centrally thus maintaining a two-dimensional axi-symmetric flow pattern. It is found that as a result of variations in the gas flow and thermal patterns in the four configurations examined (viz cylinder-on-cone, conical, hour-glass shaped, and lantern-shaped axi-symmetric) the droplet trajectories, residence times, and drying times vary. It was noted that the effective chamber volume occupied by drying particles depends on the chamber design.     

团聚液雾化气泡粒径分布特性的可视化研究

泡沫团聚法是有效脱除细颗粒物PM_2.5的方法。本文对团聚液的雾化粒径进行了研究,筛选出适于团聚PM_2.5的气泡粒径的溶液及喷雾条件。文中首先对气泡粒径与团聚颗粒物的能力进行估算,进而通过CCD拍摄精细雾化喷嘴喷出的团聚液泡沫的流动过程,利用MATLAB处理图片,得出雾化气泡粒径和密度大小。实验结果表明,发泡剂会使团聚液的雾化液滴形成气泡,增大雾化颗粒直径;PAM团聚液形成的气泡粒径偏小,且雾化颗粒密度大,粒径主要分布在小于200μm范围;XTG团聚液气泡粒径偏大,CMC团聚液气泡粒径介于两者之间;0.2% CMC团聚液气泡粒径均匀,颗粒数量大;在距喷口轴向20cm处,气泡破碎和聚合趋于稳定;喷口直径0.5mm时,气泡雾化粒径大多分布在100~300μm粒径范围内,符合团聚脱除PM_2.5的气泡条件;随着温度的升高,直径在0~300μm内的气泡颗粒数量增大明显。