Tuesday, June 30, 2020

Simulated moving bed technology from concept to operation - Free Essay Example

1. Introduction 1.1. Continuous counter current chromatography Continuous industrial-scale adsorption processes are well known for their efficiency. Very often, the Height Equivalent of a Theoretical Plate (HETP) in a batch operation is roughly three times higher than one find for the continuous mode (Gembicki et al., 2002). The operation of continuous chromatographic counter current apparatus (here-by referred as True Moving Bed, TMB) in particular, maximizes the mass transfer driving force providing a better utilization of the adsorbent, and thus, allowing the use of lower selectivity materials (Ruthven and Ching, 1989) as to operate with an increased productivity (i.e., higher processed throughput using less packing material). A scheme of a TMB unit is shown in Figure 1. Figure 1 A four section True Moving Bed (TMB) unit for the separation of A and B with D as eluent or desorbent (Fructose/Glucose separation). If we define section as the part of the TMB unit where the fluid flow rate is approximately constant (section limited by inlet/outlet streams), then, it is possible to find four different sections with different roles: Section I: Regeneration of the adsorbent (desorption of A from the solid); Section II: Desorption of B (so that, the extract is not contaminated by the less retained component); Section III: Adsorption of A (raffinate clean from the more adsorbed species); Section IV: Regeneration of the eluent/desorbent (adsorption of B from the fluid phase). From Figure 1, one can observed that the counter-current movement of the solid, with respect to the fluid phase, allows continuous regeneration of both the adsorbent in section I as the eluent/desorbent in section IV. Also, the moving bed arrangement allows the achievement of high purity even if the resolution of the two peaks is not excellent, since only the purity at the two tails of the concentration profiles, where the withdrawal ports are located, is of interest. This is contrary to batch chromatography where high resolution is vital in order to achieve high purity. Nevertheless, with this counter current mode of operation is necessary to circulate not only the fluid phase but also the solid. The solid motion inside of the column and the consequent recycle presents some technical problems, namely: equipment abrasion, mechanical erosion of adsorbent and difficulties in maintaining plug flow for the solid (especially in beds with large diameter). From a technical point of view, this clearly limits the implementation of such technology. 1.2. The Simulated Moving Bed (SMB) concept In order to avoid this issue, a sequence of fixed bed columns was conceived (Broughton and Gerhold, 1961) in which the solid phase is at rest in relation to a fixed referential, but where a relative movement between both phases is experienced by switching the inlet and outlet fluid streams to and from the columns from time to time (in the direction of the fluid flow). In the simplest operating mode, the period that a certain operating configuration prevails is called the switching time, . Since the solid flow is avoided, although a kind of counter-current movement is created relatively to the fluid, this technology is called Simulated Moving Bed (SMB). Consider that at certain moment in the operation of an SMB, the positions for the inlet of feed and desorbent and outlet of products is represented by Figure 2a. Assume also the simplest operating mode (synchronous advance of all streams) and one column per section. After a period of time equal to the switching time, the injection and withdrawn points all move one column in the direction of the fluid flow (Figure 2b). When the initial location of injection/collection of all the streams is reencountered, we have completed one cycle (in a four equally zoned SMB, it takes to complete one cycle, where is the number of columns in each one of the four sections). As it is possible to see in Figure 2, during one cycle the same column is in different sections, assuming therefore different roles in the separation process. Figure 2 Schematic representation of a 4 columns SMB unit operating over a complete cycle, from 0to (with representing the ports switching time); (a) period of the first switch; (b) period of the second switch and (c) a TMB unit. As mentioned before, the continuous movement of inlet and outlet lines into and from the column is almost impractical, therefore discreet jumps (with the length of one bed, during ) have to be applied. The analogy between SMB and the TMB is then possible by the introduction of the relative velocity concept, where , with the fluid interstitial velocity in each section in the TMB, the interstitial velocity in the SMB unit and the solid interstitial velocity in the TMB. The solid velocity is evaluated from the switching time interval value in the SMB as , being the column length. As consequence, The internal flow rates in both apparatus are not the same, but related by where and represent the internal liquid flow-rates in the SMB and TMB, respectively, is the bulk porosity and the column volume. 1.3. SMB Applications Industrially, SMB applications can be regarded as Old and New, associated with petrochemical and pharmaceutical/fine chemistry fields, respectively (S Gomes et al., 2006d). Among the first applications of SMB technology (back to 1960s) are the ones implemented by the UOP Inc. (Des Plaines, IL-USA) with the Sorbex processes, such as: the Parex unit for separation of p-xylene from mixtures with its C8-isomers (Broughton et al., 1970), separation also performed by the Aromax process from Toray Industries (Tokyo, Japan) (Otani et al., 1973) and the Eluxyl process by Axens/IFP (Institut Franais du Ptrole, France) (Ash et al., 1994); the Ebex for the separation of EthylBenzene (EB) from a mixed of C8-aromatic isomers (Broughton, 1981); the Molex for the separation of n-paraffins from branched and cyclic hydrocarbons; and the Olex process to separate olefins from parafins; the Cresex and Cymex for the separation of p-cresol and p-cymene from its isomers, respectively. The application of SMBs in the sugar industry is also substantial, with the Sarex process, for the separation of fructose from the corn syrup with dextrose and polysaccharides on polystyrene-divinylbenzene resins in calcium form (Broughton, 1983); or as patented by Japan Organo Co. (Japan), (Heikkil et al., 1989); by Amalgamated Sugar Company LLC, also known as the Snake River Sugar Company (Boise, ID-USA), (Kearney and Mumm, 1990, , 1991). In the last decade, particularly in the area of drug development, the advent of SMB has provided a high throughput, high yield, solvent efficient, safe and cost effective process option. Although it had long been established as a viable, practical, and cost-effective liquid-phase adsorptive separation technique, the pharmaceutical and biomolecule separations community did not show considerable interest in SMB technology until the mid-1990s. The application of the SMB concept to the fine chemical separations in the earlier 90s, led to the second boom on the number of applications of SMB technology (Negawa and Shoji, 1992; Nicoud et al., 1993; Kusters et al., 1995; Rodrigues et al., 1995; Cavoy et al., 1997; Francotte and Richert, 1997; Guest, 1997; Pais et al., 1997a; Pais et al., 1997b; Francotte et al., 1998; Grill and Miller, 1998; Lehoucq et al., 1998; Pais et al., 1998; Dapremont et al., 1999; Miller et al., 1999; Nagamatsu et al., 1999; Nicoud, 1999a, 1999b; Pedeferri et al., 19 99; Strube et al., 1999; Juza et al., 2000; Kniep et al., 2000; Wang et al., 2001), among other pioneers. Daicel Chemical Industries, Ltd (Japan) first published the resolution of optical isomers through SMB (Negawa and Shoji, 1992). Since then, several are the SMB based processes already approved by the Food and Drug Administration (FDA) and others regulatory agencies. Examples includes renowned products such as: Biltricide (Praziquantel) Cipralex/Lexapro (Escitalopram), Keppra (Levetiracetam), Modafinil/Provigil, Taxol (Paclitaxel), Xyzal (Levocetirizine), Zoloft (Sertraline), Zyrtec (Cetirizine), Celexa/Citrol/Cipram (Citalopram), Prozac (Fluoxetine hydrochloride), (Abel and Juza, 2007) o paper de real SMB e rajendran, among others biological separation, with a particular emphasis in protein separations meteer referencias a biologias e proteinas. Given the importance of such technique, this work reviews different operating SMB modes; design, modeling and optimization techniques; and addresses an example of the design, construction and operation of an SMB unit. 2. SMB modes of operation So far, only the so-called conventional SMB mode of operation has been considered, which indeed means that each section has a fixed number of columns and there is no variation on the pre-established inlet/outlet flow rates or the switching time value. However, over the last decades some non-conventional SMB operating modes were proposed, developing the range of the applications of SMB technology and extending further its potential. Some of these operating modes, worthy of note, are listened in the following Sections. 2.1. Asynchronous shifting SMB (the Varicol process) The asynchronous shifting SMB or Varicol process (Adam et al., 2000; Bailly et al., 2000; Ludemann-Hombourger et al., 2000; Ludemann-Hombourger et al., 2002) commercialized by Novasep (Pompey, France), became one of the more studied and used processes of the so-called non-conventional SMB modes of operation. Instead of a fixed unit configuration with constant section length, the Varicol operating mode is performed by the implementation of an asynchronous inlet/outlet ports shift, providing a flexible use of each section length, Figure 3. Figure 3 [11.51.51] Asynchronous SMB for a complete cycle; section II has 1 column during the first half of the switching time and 2 columns in the remaining time (within a switching time period), thus 1.5 columns; the opposite happens to section III. By means of Varicol mode of operation it is possible to increase the productivity value up to 30% more than the classical SMB apparatus, principally when operating under a reduced number of columns (Toumi et al., 2002; Zhang et al., 2002b; Pais and Rodrigues, 2003; Subramani et al., 2003b, 2003a; Toumi et al., 2003; Yu et al., 2003b; S Gomes et al., 2006d; Mota et al., 2007b; Rodrigues et al., 2007a; S Gomes et al., 2007b; Zhang et al., 2007). 2.2. Partial-Feed, Partial-Discard With the Partial-Feed mode of operation two additional degrees of freedom are introduced: the feed length and the feed time (Zang and Wankat, 2002a; Zang and Wankat, 2002b). Feed during a given feed length period will consequently influence the raffinate and extract flow rates are along the time. Also referred in the literature is the Partial-Discard (or partial withdraw) operating mode, where just a part of the outlet products is used in order to improve the overall purity (Zang and Wankat, 2002b; Bae and Lee, 2006), or with the partial recirculation of the outlet products back to the feed (Kessler and Seidel-Morgenstern, 2008a; Kessler and Seidel-Morgenstern, 2008b; Seidel-Morgenstern et al., 2008). The ISMB (Improved SMB) mode of operating, commercialized by the Nippon Rensui Co. (Tokyo, Japan) and FAST Finnsugar Applexion Separation Technology, now Novasep-France, is also well known (Tanimura et al., 1989). In this process, during a first step the unit is operated as a conventional SMB but without any flow in section IV; in the second step the inlet and outlet ports are closed and the internal flow through the four sections allowing the concentration profiles to move to adjust their relative position with respect to the outlet ports (Rajendran et al., 2009). Meter referencias do mazzotti e nova de sa gomes Another novel non-conventional mode of operation, the Outlet Swing Stream-SMB (OSS) (S Gomes and Rodrigues, 2007), was developed under the framework of this thesis and is latter detailed in Chapter 3. 2.3. PowerFeed and ModiCon The modulation of the section flow rates (PowerFeed) was originally proposed by Kearney and Hieb (1992) and later studied in detail by other authors (Kloppenburg and Gilles, 1999b; Zhang et al., 2003b; Zhang et al., 2004b; Kawajiri and Biegler, 2006b). Another SMB operating concept, based on the feed concentration variation within one switching interval, was suggested by Schramm et al., (2002; 2003b) known as the ModiCon. The use of auxiliary feed tanks, where section flow rate flows into a tank to dissolve solid raw materials and fed into section III, has also been studied (Wei and Zhao, 2008). The cross combination of PowerFeed, Modicon and Varicol modes of operation is also a recurrent research matter, principally of optimization studies (Zhang et al., 2004a; Arau?jo et al., 2006a; Rodrigues et al., 2007b), providing more degrees of freedom and allowing better performance values. 2.4. Two Feed or MultiFeed SMB and Side Stream SMB Recently, the introduction of multi feed streams in the SMB area, by analogy with distillation columns, led to the formulation of the Two Feed SMB, or MultiFeed, operating mode presented by Kim (2005) and later studied by S Gomes and Rodrigues (S Gomes et al., 2007b; S Gomes and Rodrigues, 2007). Also multi extract/raffinate are referred in the literature (Mun, 2006), known as side stream SMB (Beste and Arlt, 2002). These techniques, combined with the distillation know-how for the optimum location of multiple feeds, can allow the development of more efficient SMB processes. 2.5. Semi Continuous, Two and Three zones SMB There are several semi continuous SMB apparatus that operate with two-zone, two or one-column chromatograph, with/or recycle, analogous to a four-zone SMB(Abunasser et al., 2003; Abunasser and Wankat, 2004; Arau?jo et al., 2005a; Arau?jo et al., 2005b; Jin and Wankat, 2005b; Mota and Arau?jo, 2005; Arau?jo et al., 2006b; Arau?jo et al., 2007; Rodrigues et al., 2008b), that allow a reasonable separation, some allowing centre cut for ternary or quaternary separations (Hur and Wankat, 2005b, 2005a, , 2006a, 2006b; Hur et al., 2007), under reduced equipment usage. The discontinuous injection in a system with 2 or more columns, based on the concept of simulated adsorbent movement, as been applied by Novasep under the denomination of Cyclojet, Hipersep, Supersep (Supersep MAX with Super Critical CO2) and Hipersep, (Grill, 1998; Valery and Ludemann-Hombourger, 2007). 2.6. Gradient SMB As a further possibility for increasing the productivity, the introduction of gradients in the different separation sections of the SMB process is also described in literature. The gradient mode was suggested firstly for the SMB-SFC (SMB-supercritical fluid chromatography) process, where the elution strength can be influenced by a pressure gradient (Clavier and Nicoud, 1995; Clavier et al., 1996). Nowadays, there are more gradient-variants that allows the variation solvent elution strength by changing the temperature, the pH-value, the content of salt or the modifier concentration (Jensen et al., 2000; Antos and Seidel-Morgenstern, 2001; Migliorini et al., 2001; Abel et al., 2002; Antos and Seidel-Morgenstern, 2002; Abel et al., 2004; Ziomek and Antos, 2005; Mun and Wang, 2008a), or as in Rodriguess group with the purification of proteins by Ion Exchange-SMB (IE-SMB) (Li et al., 2007; Li et al., 2008). Also worth of note is the MCSGP (Multicolumn Counter-current Solvent Gradient Puri fication) process (Aumann and Morbidelli, 2006; Strohlein et al., 2006; Aumann and Morbidelli, 2007; Aumann et al., 2007; Aumann and Morbidelli, 2008; Mller-Spth et al., 2008), commercialized by ChromaCon AG (Zrich, Switzerland), which combines two chromatographic separation techniques, the solvent gradient batch and continuous counter-current SMB for the separation of multicomponent mixtures of biomolecules. 2.7. Hybrid-SMB: SMB combined with other processes It is possible to improve the performance of SMB units by integrating it with other different separation techniques. The more simple application of this approach is to combine in series the two different processes and then recycle back the outlets between (or within) the different units (Lorenz et al., 2001; Amanullah et al., 2005; Kaspereit et al., 2005; Amanullah and Mazzotti, 2006; Gedicke et al., 2007). Among these, an interesting hybrid SMB was presented by M. Bailly et al., (2005; Abdelmoumen et al., 2006), the M3C process; or the similar process: Enriched Extract operation (EE-SMB) (Paredes et al., 2006), in which a portion of the extract product is concentrated and then re-injected into the SMB at the same, or near to, the collection point. The use of SMB-PSA apparatus is also referred in the literature for gas phase separations, (Rao et al., 2005; Sivakumar, 2007; Kostroski and Wankat, 2008). The use of two SMB units with concentration steps between, for the separation of bi nary mixtures, was also developed under the denomination of hybrid SMB-SMB process (Jin and Wankat, 2007a). 2.8. The SMBR multifunctional reactor The integration of reaction and separation steps in one single unit has the obvious economical advantage of reducing the cost of unit operations for downstream purification steps. Besides reactive distillation, reactive extraction or membrane reactors, the combination of (bio)chemical reaction with SMB chromatographic separator has been subject of considerable attention in the last 15 years. This integrated reaction-separation technology adopts the name Simulated Moving Bed Reactor (SMBR). Several applications have been published considering the SMBR: the enzymatic reaction for higher-fructose syrup production (Hashimoto et al., 1983; Azevedo and Rodrigues, 2001; Borges da Silva et al., 2006; S Gomes et al., 2007a); meter a dos FOS the esterification from acetic acid and -phenethyl alcohol and subsequent separation of the product -phenetyl acetate (Kawase et al., 1996), or methyl acetate ester (Lode et al., 2001; Yu et al., 2003a); the synthesis and separation of the methanol from sy ngas (Kruglov, 1994); the esterification of acetic acid with ethanol (Mazzotti et al., 1996b); the lactosucrose production (Kawase et al., 2001); the MTBE synthesis (Zhang et al., 2001); the diethylacetal (or dimethylacetal) synthesis (Silva, 2003; Rodrigues and Silva, 2005; Silva and Rodrigues, 2005a; Pereira et al., 2008); the ethyl lactate synthesis from lactic acid and ethanol (Pereira et al., 2009a; Pereira et al., 2009b); the biodiesel synthesis (Geier and Soper, 2007) falta uma; or the isomerization and separation of p-xylene (Minceva et al., 2008) faltam os franceses, are examples that prove the promising potential of this technique. Depending on the reactive system some interesting arrangements of the general SMBR setup can be found in the literature, a more detailed review of several SMBR applications can be found elsewhere (Minceva et al., 2008). 2.9. Multicomponent separations The application of SMB technology to multicomponent separations has also been an important research topic in the last years. The common wisdom for such multicomponent process is the simple application of SMB cascades (Nicolaos et al., 2001a, 2001b; Wankatt, 2001; Kim et al., 2003; Kim and Wankat, 2004); nevertheless, there are some non-conventional operation modes that proved to have interesting performance, as the one introduced by the Japan Organo Co. (www.organo.co.jp), called JO process (or Pseudo-SMB); this process was discussed in detail (Mata and Rodrigues, 2001; Borges da Silva and Rodrigues, 2006, , 2008) and (Kurup et al., 2006a). The process is characterized by a 2-steps operation: (a) in the first step the feed is introduced while the intermediary product is recovered with the whole unit working as a fixed bed; (b) during the second step the feed stopped, the unit works as a standard SMB and the less and more retained products are collected, see Annex I for details. The u se of two different adsorbents (Hashimoto et al., 1993), two different solvents (Ballanec and Hotier, 1992), or a variation of the working flow rates during the switching period (Kearney and Hieb, 1992), were also proposed. 2.10. SMB Gas and Super Critical phases Most of the industrial applications of SMB technology operate in the liquid phase; nevertheless, SMBs can also be operated under supercritical conditions; where a supercritical fluid, typically CO2, is used as eluent offering a number of advantages namely reduction of eluent consumption, favourable physicochemical properties and lower pressure drop and higher column efficiency (Clavier and Nicoud, 1995; Clavier et al., 1996; Denet and Nicoud, 1999; Depta et al., 1999; Denet et al., 2001; Johannsen et al., 2002; Peper et al., 2002; Peper et al., 2007). Also in the gas phase the recent developments have been remarkable (Storti et al., 1992; Mazzotti et al., 1996a; Juza et al., 1998; Biressi et al., 2000; Cheng and Wilson, 2001; Biressi et al., 2002; Rao et al., 2005; Lamia et al., 2007; Mota et al., 2007b; Sivakumar, 2007; Kostroski and Wankat, 2008). Meter a do propano propylene 3. SMB design, modeling, simulation and optimization Over the last 50 years, design, modeling, and optimization of chromatographic separation processes have been frequent research subjects. As consequence, several modeling methods, strategies and approaches have been developed, the more relevant are reviewed in this section. 3.1. Design strategies The design of an SMB based separation involves taking decisions at many levels, from the configuration of the unit (number of columns per section, column and particle size) to operating conditions (feed concentration, switching time, internal flow rates). Although simulation can be exhaustively done until the right combination of parameters is found for the expected performance, it is useful to have a design method that will provide a preliminary estimation of the optimum operating point, followed by simulation and/or optimization, (S Gomes et al., 2009a). The equivalence between TMB and SMB can be quite useful in the SMB design procedure. Recalling the role of each SMB section (Figure 2c), one can state a set of constraints that will limit the feasible region and allow a complete separation (recover of the more retained species (A) in the extract stream, the less retained one (B) in the raffinate port, and regeneration of the solid in section I as fluid in section IV). Where represents the solid flow rate, the average solid concentration of species in section and the bulk fluid concentration of species in section . The flow rates constraints in Eq. 1b and 1.c will identify the separation region (section II and III), while Eq. (1 a) and Eq. (1 d) the regeneration one (section I and IV). Usually, the fluid and solid velocities in each section are combined into one only operating parameter, such as the from Morbidellis group or the , as used by Ruthven (1989). The identification of constrains, Eq. (1 a) to Eq. (1 d), led to the appearance of several design methodologies, which are usually approximated and/or graphical, providing a better insight to the possible operating regions. From the plates theory and McCabe-Thiele diagrams (Ruthven and Ching, 1989); passing by the analytical solutions for a linear adsorption isotherms system in presence of mass transfer resistances (Silva et al., 2004); to the determination of waves velocities as in the Standing Wave Design (SWD) methodology (Ma and Wang, 1997; Mallmann et al., 1998; Xie et al., 2000; Xie et al., 2002; Lee et al., 2005). A particular emphasis should be given to the strategy developed for binary and multicomponent separations modeled by linear and non-linear isotherms as in (Storti et al., 1989b; Storti et al., 1 993; Mazzotti et al., 1994; Storti et al., 1995; Mazzotti et al., 1996c; Mazzotti et al., 1997b; Chiang, 1998; Migliorini et al., 2000; Mazzotti, 2006b), the so-called Triangle Theory, where the term is treated by assuming that the adsorption equilibrium is established everywhere at every time (Equilibrium Theory, (Helfferich, 1967; Klein et al., 1967; Tondeur and Klein, 1967; Helfferich and Klein, 1970), resulting in a feasible separation region formed by the above constraints Eq. (1 b) and Eq. (1 c), which in the case of linear isotherms takes the shape of a right triangle in the plane, Figure 4, (or a triangle shaped form with rounded lines in non-linear isotherms case), and a rectangular shape in the plane. Recently, this methodology was also extended for the design of SMB units under reduced purity requirements, in which the separation triangle boundaries are stretched to account for different extract and/or raffinate purities (Kaspereit et al., 2007; Rajendran, 2008). Figure 4 Triangle Theory, separation and regeneration regions for linear isotherms, where represents the Henry constant for linear adsorptions isotherms (A: the more retained and B: the less retained species), is the intraparticle porosity; case of (S,R)Tetralol enantiomers, see Section 4.3.2. Nevertheless, the inclusion of mass transfer resistances can deeply affect the result of the design. By taking into account all mass transfer resistances, and running successive simulations, it is possible obtain more detailed separation/regeneration regions, as well as the separation study carried out for three different sections (II, III and I) or (II, III and IV) allowing the analysis of solvent consumption or solid recycling, as proposed in the Separation Volume methodology, (Azevedo and Rodrigues, 1999; Rodrigues and Pais, 2004a), or the influence of the solid flow rate in the separation region (Zabka et al., 2008a). 3.2. Modeling and simulation Generally, one can model a chromatographic separation process, and consequently an SMB unit, by means of two major approaches: by a cascade of mixing cells; or a continuous flow model (plug flow or axial dispersed plug flow, making use of partial differential equations derived from mass, energy and momentum balances to a differential volume element ), (Rodrigues and Beira, 1979; Ruthven and Ching, 1989; Tondeur, 1995; Pais et al., 1998). Each of these approaches can include mass transfer resistances, thermal, and/or pressure drop effects. Nevertheless, most of the recent literature concerning SMB processes just makes use of the continuous approach, detailing the particle diffusion and/or film mass transfer (the Detailed Particle Model), or using approximations to the intraparticle mass transfer rate in a similar way as the Linear Driving Force (LDF) approach presented by Glueckauf (1955a), (Guiochon, 2002). One can argue that an SMB unit is no more than the practical implementation of the continuous counter current TMB process, Figure 2. Consequently, the equivalence between the TMB and a hypothetical SMB with an infinite number of columns can be used in the modeling and design of SMB units. However TMB model approach will just give reasonable results if a considerable number of columns per section is present. The SMB model approach represents an SMB unit as a sequence of columns described by the usual system equations for an adsorptive fixed bed (each column ), thus represented by a PDE system. Nevertheless, the nodes equations can be stated to each section, making use of the equivalence between the interstitial velocity in the TMB and SMB, and thus: The issue here is that, due to the switch of inlet and outlet lines, the boundary conditions to a certain column are not constant during a whole cycle but change after a period equal to the switching time. Since the model equations are set to each column , one will obtain the concentration of species in the begin of each section , , from the following node mass balances: Considering now . This set of equations continues to progress in a similar way (shifting one column per ), until , repeating then from the first switch. As for the TMB model approach, both the Detailed Particle Model and LDF approach can be used with the SMB model approach; nevertheless, and for the sake of simplicity, just the last is detailed in this work. The LDF approximation can now be obtained from , and thus obtaining for the bulk fluid mass balance: and for the mass balance in the particle, with the respective initial: and boundary conditions: where the adsorption equilibrium isotherm is: As a consequence one obtains discontinuous solutions, reaching not a continuous Steady State but a Cyclic Steady State (CSS). By applying the SMB model approach, both the Detailed Particle as LDF strategies, to the case study mentioned before, one obtains the CSS concentration profiles over a complete switching time, Figure 6. 3.3. Performance parameters The performance of the SMB unit for a given separation is usually characterized by the following parameters: purity, recovery, productivity per the amount adsorbent volume and eluent/desorbent consumption per mass of treated product. The definitions of all these performance parameters, for the case of a binary mixture, are given bellow: Purity (%) of the more retained (A) species in extract and the less retained one (B) in the raffinate stream, over a complete cycle (from to ): Recovery (%) of more retained (A) species in extract and the less retained one (B) in raffinate stream, again over a complete cycle: the productivity per total volume of adsorbent : the eluent/desorbent consumption : These parameters hold for both SMB and TMB model approaches; nevertheless, one can simplify: in the SMB model strategy the same equations can be stated for a switching time period (from to ) if the unit is symmetrical, i.e., there are no differences between each switching time period (either due to the implementation of non-conventional modes of operation, or to the use of more detailed models accounting for dead volumes or switching time asymmetries); in the TMB model approach there is no need of the integral calculation, since the solutions from this model strategy are continuous and thus, the performance parameters constant over the time (at the steady state). 3.4. Optimization Usually one can classify the optimization of SMB units according to the type of objective functions: (i) optimization of performance parameters (productivity, adsorbent requirements or desorbent/eluent consumption for given purities and/or recovery requirements); (ii) optimization based on the separation cost. In case (i) each objective function, based on a different set of performance parameters, can lead to a different optimum solution; therefore multi-objective functions procedure should be considered; in the second case (ii) all those different performance parameters can be homogenized/normalized by the separation cost, where separation dependent costs (adsorbent, plant, desorbent/eluent recovery cost, desorbent/eluent recycling, feed losses) and separation independent costs (wages, labour, maintenance, among others) are taken into account and weighted by cost factors, which sometimes are difficult to characterize (Jupke et al., 2002; Chan et al., 2008). To solve these problems, the use of powerful optimization algorithms, such as: IPOPT (Interior Point OPTimizer, (Wa?chter and Biegler, 2006), employed for liquid as gas phase SMB separations (Kawajiri and Biegler, 2006b, 2006a; Mota et al., 2007a; Mota and Esteves, 2007; Rodrigues et al., 2007b; Kawajiri and Biegler, 2008a, 2008b); the commercial package gOPT from gPROMS with a Single (or Multiple) Shooting-Control Vector Parameterization, used in the two level optimization of an existing Parex unit (Minceva and Rodrigues, 2005), for ageing analysis (S Gomes et al., 2008b) and gas phase separation of propane/propylene (S Gomes et al., 2009a) or for optimal economic design (Chan et al., 2008); the Non-dominated Sorting Genetic Algorithm (NSGA) or the Jumping Gene based algorithms (Deb, 2001), such as NSGA-II-JG, applied by several groups to optimize SMB units, from p-xylene to chiral separations (Zhang et al., ; Zhang et al., 2002a; Subramani et al., 2003b; Zhang et al., 2003a; Wongso et al., 2004; Kurup et al., 2005; Wongso et al., 2005; Kurup et al., 2006c; Paredes and Mazzotti, 2007; Lee et al., 2008; Mun and Wang, 2008b), is recurrent, either in the refinement of the design strategies mentioned before, or as a diagnosis method (such as the use of superstructures SMB considering several hypothetic inlet/outlet recycles), allowing the identification of new SMB configurations or modes of operation. 4. Design, construction and operation of SMB units The design, construction and operation of a new lab-scale flexible SMB unit, the FlexSMBLSRE detailed elsewhere (aper aiche sa gome), is addressed in this section. 4.1. Design and construction 4.1.1. Valves and pumps design As mentioned before, there are several ways to operate an SMB unit; therefore, when designing a new SMB unit, particularly for research purposes, one should take into account its flexibility as a key objective (Chin and Wang, 2004). If one considers an SMB unit as a certain number of packed columns interconnected and feedcontrolled by a specific valves and pumps arrangement, it will be easy to understand that the key factor related with an SMB unit expandability and flexibility is in fact its valves system. An extensive review on the different SMB units valves schemes patented over the years can be found elsewhere (Chin and Wang, 2004). The FlexSMB-LSRE is based on a two SD (SelectDeadend flow path) valves per stream in the extract and raffinate currents, one SD per stream in the feed and eluent/desorbent currents and one twoway valve per column as detailed in Figure 6.2. Figure 6.2 FlexSMB-LSRE pumps and valves scheme under a 6 columns configuration, operating a during the first step of a [1221] classic SMB. Bold lines are the active connections; thick lines are stagnant volumes. (alterar a figura) By using this valves and pumps scheme, it is possible to operate most of the non-conventional SMB operating modes and perform columns re-configuration simply by changing some parameters in the automation routines on the computer interface. 4.1.2. Construction When assembling an SMB unit one should take into account that tubing and other equipment will introduce dead volumes; pumps and valves distribution may introduce dead volumes asymmetries, and thus the unit might present in the end some peculiarities which can limit its performance. Therefore, when constructing the FlexSMB-LSRE a preliminary work was undertaken to study possible equipment and columns positing. As result, the tubing and equipment dead volumes were reduced by using of 1mm i.d. tubes and short dead end valves (SD, Valco Instruments Co., Inc.) were employed. To reduce the dead volumes asymmetries, tubes with the same length were used for the same function and all columns assembled in a carousel scheme, Figure 6.4. Photo do SMB To reduce the pumps flow rates fluctuations (fluid inlets, outlets and internal flow rates), four HPLC pumps (VWR International, USA) were used, assisted by two Coriolis flow meters (Bronkhorst High-Tech B.V., Netherlands). One purge valve was installed at the outlet of raffinate stream that together with a purge valve installed next to the extract pump serves to manually regulate the total system pressure, as well as security valves. To avoid variations related to the ports switching velocity asymmetries a distributed connection scheme for the SD valves was used. The FlexSMB-LSRE can operate with a maximum number of columns of 12. For a 6 columns apparatus, all columns were connected to the 12 ways SD valves using just the odd valve connecting positions (i.e., 1,3,,9, 11) in order to reduce the switching time discrepancies. All equipment is connected to an integrated power supply that assures protection from electrical fluctuations as a possible current discharge. 4.1.3. Automation The automation of any laboratorial/industrial unit is a critical task, and as it concerns to an SMB unit, it is probably even more crucial. In fact, a relevant part of these units flexibility relies in its automation and control routines. The LabView (National Instruments, USA) platform, was chosen to automate the FlexSMB-LSRE unit and thus to connect the computer to all controllable equipment: (valves, pumps and flow meters). A LabView based application was then used to provide a user friendly interface between the operator and the equipment, Figure XX. 4.1.4. Columns packing and characterization The common modeling strategies assume that all SMB columns have identical characteristics. However, it is quite difficult to find several columns manufactured with the same specifications (column tubes may have slightly different geometric dimensions, thus, different retention times for a given flow rate), as well as one should take into account that packing procedure is quite irreproducible, and therefore, it results on local fluctuations of the packing density) (Mihlbachler et al., 2001; Mihlbachler et al., 2002). Consequently, once the operator introduces the theoretical optimized operating parameters, the differences between columns arise and different values from the ones expected can appear. Therefore, packing of SMB columns should be carefully done and columns should be repacked if do not present acceptable reproducibly good characterization results. For the FlexSMB-LSRE columns used for the case studies presented in the next Sections, the slurry packing method as chosen and each column packed by means of Analytical Slurry Packer from Alltech Associates Inc. (USA). For each column a slurry of approx. 18.5g of Chiral AD 20m, amylose tris-(3,5 dimethylphenylcarbamate coated onto 20m silica-gel), provided by Chiral Technologies Europe (France) in approx. 36ml of 2-propanol (GC-grade from Sigma-Aldrich Chemie, Germany) was prepared (pure 2-propanol was chosen as slurry solvent taking into account its physical proprieties, namely its viscosity). For the case studies shown on this work, The column was filled with solvent (2-propanol) and the slurry poured its upper reservoir. Then, the analytical slurry packer pump was connected to the upper reservoir and operated for 10min, at a max solvent pressure of 20bar (approx. 300ml.min-1), the solvent used was a mixture of -hexane/2-propanol, 90/10%, volumetric fraction, (GC-grade from Sigma-A ldrich Chemie, Germany). The reservoir was opened and the excess solvent drained again; the column disconnected from the reservoir and the excess of solid in the top of the column cut with a blade. Each column was evaluated for HETP numbers, tracer experiments were performed by injecting pulses of 100ml of a solution of 0.00667+/-0.00001g of TSO (Trans Stilbene Oxide, racemic mixture standard for this type of operations) and 0.00700+/0.00001g of TTBB (1,3,5 TriTert ButyBenzol, considered non adsorbed) in 25.00+/-0.05ml of heptane-2-propanol (95%-5%, volume fraction) mobile phase. An average HETP value of 0.03cm was found and the retention times obtained from the experiments has a maximum deviation of 5% among all the columns. Therefore, and accounting with the packing supplier specifications, the columns were considered suitable for the SMB operation. 4.2. Operation The technology demonstration stage is a quite important step in the RD flow sheet, and in fact, when it accounts to equipment development it is probably the most important one. To operate and demonstrate some of the potential of the FlexSMB-LSRE unit, a set of different experiments was planned regarding both linear as non-linear adsorption isotherms, under different modes of operation (classic and non-conventional). However, the operation of SMB units is not as straightforward as other batch techniques, and a particular attention must also be directed for some aspects not accounted (or simplified) in the modeling stage. 4.2.1. Real SMB units modeling and design It should be taken into account that the performance of a real SMB unit differs from the ones described by the commonly used modeling and design strategies. There are several factors that can influence the precision of the SMB model predictions, such as: uncertainty in adsorption equilibrium kinetics and hydrodynamics data (diffusivity, axial dispersion coefficients etc.) and bed voidage (packing asymmetries), as well as, extra column dead volumes (tubing, equipment, asymmetries), variation in the port switching velocity (asymmetries and delays), fluctuations in pump flow rates (fluid inlets, outlets and internal), which are not accounted for it in the most commonly used SMB models (Mun et al., 2006). Consequently, if one runs an experimental SMB unit based on the operating parameters obtained by a simple mathematical model, such as the one described in Section CCC, the experimental results may not match the ones that were predicted by the model. Concerning the uncertainty in the equilibrium isotherm data, kinetics data, and even the asymmetries of columns packing, the more precise, and/or accurate, these factors are, better will be the SMB model predictions. Therefore, detailed and precise measurements of all these parameters have to be done a priori, so that they introduce a minimal discrepancy between the SMB model results and the experiments itself. The remaining deviation factors, such as the tubing and equipment dead volumes, pumps and valves asymmetries, related to each SMB unit design and equipment particularities should be taken into account before starting to construct a new SMB unit, as detailed before. However, even after all the work done on the FlexSMB-LSRE unit, the unit still has: 11.5% of dead volumes; the port switching velocity variation (delay) can represent around 0.8 seconds; the fluctuation of the pumps flow rates are still considerable. If the average internal flow rates in each section are kept constant during the SMB operation (as assumed by some SMB design procedure) the SMB performances would not be affected, despite their considerable local variations. This is due to the cyclic mode of operation of these units, leading to compensation of these variations with time. Nevertheless, there are still two major issues concerning the prediction of the SMB performances: the unit SMB design features related with the dead volumes and the switching time asymmetries or delay. To deal with discrepancies between the real SMB operation and that predicted with commonly used models that account only for the presence of SMB columns (and do not consider the surrounding equipment features) one can apply different compensation strategies. For instance, the asynchronous port shift in the Licosep units (Hotier and Nicoud, 1995; Hotier and Nicoud, 1996; Blehaut and Nicoud, 1998), and simplified by switching time compensating strategy ( Sa gOmes). The second strategy was discussed by several authors, within the Triangle Theory spectrum (Migliorini et al., 1999b; Katsuo et al., 2009), or in the case of the Standing Wave Theory (Mun et al., 2003a; Mun et al., 2006). The switching time compensating measure accounts only for equipment dead volumes, the switching time delay or asymmetry is still not compensated when this measure is used. They can be included in the switching time compensation measure as true delay in the switching time, as follows: For the FlexSMB-LSRE: Where represents the switching time for an ideal SMB unit with zero dead volumes, the total dead volumes in section , ml.min1, the units average flow rate and the sub switching time delay (see Figure 6.14). The corrected separation region using the extension to the switching time compensating measure is shown in Figure 6.17. As can be observed in Figure 6.17, the SMB-zero dead volumes separation region corrected by the dead volumes and switching time delay (asymmetries) almost matches the one obtained with the detailed model. By this means it is possible to easily obtain a precise and realistic separation region without running tedious simulations related with the more detailed SMB models. 4.2.2. Separation of racemic mixture of (S,R)Tetralol enantiomers (linear Isotherms) by conventional SMB As case study it is presented the resolution of a racemic mixture of (S,R)Tetralol 9(S,R)-()-1,2,3,4 Tetrahydro-1-naphthol) at the concentration of 1.0g.dm3 in a heptane/2propanol (95%/5% volumetric fraction) solvent basis, using the 6 stainless steel columns packed with CSP Chiralpak AD (diameter particle size of 20m). a) Determination of adsorption and kinetic parameters Since the racemic mixture to be separated would be prepared at 1.0g.dm3, near diluted conditions, the adsorption equilibrium was represented by means of a linear formula characterized by an Henry constant for each enantiomer , . Consequently, the sorption parameters were determined by means of pulse experiments in a stainless steel column (=25cm and I.D.=0.46cm) packed with Chiralpak AD (diameter particle size of 20m) also using the Analytical Slurry Packer as described before. A racemic solution of 0.5g.dm3 (S,R)Tetralol (minimum 99% purity, Fluka Chemie, Switzerland) was prepared in a heptane/2propanol (95%/5% volumetric fraction, also from Sigma Aldrich, previously degassed and filtrated trough a 0.2m and 50mm I.D. NL 16-membrane filter (Schleicher Schuell, Germany), and loaded into a 10l loop that was then injected by means of a Knauer injection valve installed on a Gilson HPLC unit. The consequent peaks were measured by means of a UV detector set at 270nm. The procedure was rep eated for four different flow rates (4.4ml.min1; 8.5ml.min1; 12.5ml.min1; and 16.6ml.min1). The peaks retention times () were then deducted from the equipment dead volumes (0.50ml for the injector and 0.01ml for the detector) and plotted in function of the measured flow rate, Figure 6.18. The slopes obtained from both regression lines (Figure 6.18) were then used to determine the Henry adsorption constants of both enantiomers from and thus obtaining (R=A and S=B): and . The same overall mass transfer coefficient as defined in Zabka and Rodrigues (2007), was used to lump both the intraparticle as film mass transfer resistances and defined by . Where was calculated from the Linear Driving Force (LDF) approximation suggested by Glueckauf (1955b) (with the effective pore diffusivity define by , the pore porosity, , the particle porosity obtained from , the molecular diffusivity calculated by the Wilke-Chang equation (1955) and extended to mixed solvents by Perkins and Geankoplis (1969) with the absolute temperature, the solution viscosity, calculated according to Teja and Rice method for liquid mixtures (1981), the solute molar volume and obtained form where are the molar fractions, the molar masses and are the association factors constants which account for solute-solvent interactions); and obtained from , with the Sherwood number, the Schmidt number defined by and the Reynolds number: . The contribution of molecular diffusion to axial dispersion is assumed to be negligible and therefore the axial dispersion coefficient ( obtained from, (Zabka and Rodrigues, 2007). b) Determination operating parameters and operation After the determination of the equilibrium adsorption parameters it was possible to draw both the theoretical separation as the regeneration regions for the separation under study and choose suitable operating conditions, Taking into account the equipment limitations as maximum pressure drop allowable (20bar), it was possible to calculate the following operating parameters: ml.min-1, =6.0ml.min-1, =1.0ml.min-1, =4.5ml.min-1, =2.5ml.min-1, =2.95min. Applying the dead volumes and switching time delay correction (from eq. 6.3) it was found that the switching time compensating measure should be about 4% (based on an average flow rate of 25.0ml.min1), and thus correcting the switching time for 3.05min. About 5dm3 of nheptane/2propanol (95%/5% volumetric fraction) solution was prepared and filtrated as mentioned before. This mixture served as Eluent as well as solvent for the preparation of 1dm3 of the racemic mixture of (S,R)Tetralol at 1.0g.l1 used as Feed. The extract and raffinate flow rates were monitored by means of the total recovered mass in each outlet over complete cycles and weighted on a laboratorial balance with 0.01g of precision. The extract flow rate was also measured by means a Coriolis flow meter installed for control purposes at the extract stream outlet. The recycle flow rate was monitored by the other Coriolis flow meter. The experimental average flow rates, as well as geometric features, number of columns and SMB configuration are reported in Table 6.9. Table 6.9 Experimental operating conditions for the (S,R)Tetralol racemic mixture separation . Columns and packing parameters = 10cm = 2.0cm = 0.4 = 0.5g.dm3 20m SMB operating conditions (measured) 3.05min 28.7ml.min1 24.3ml.min1 25.3ml.min1 22.9ml.min1 Eluent Extract Feed Raffinate 5.8ml.min1 4.4ml.min1 1.0ml.min1 2.4ml.min1 The different model equations presented in this work were numerically solved using the gPROMS v2.3.6 a commercial package from Process Systems Enterprise (www.psenterprise.com), by applying the OCFEM (Orthogonal Collocation on Finite Elements) with 2 collocation points per element, 50 elements in each column for the axial coordinate and 3 collocation points and 5 elements for the radial discretization (when necessary). After the axial and/or radial discretization step, the time integration is performed by the ordinary differential equation solver SRADAU a fully-implicit Runge-Kutta method that implements a variable time step, the resulting system is then solved by the gPROMS BDNSOL (Block decomposition NonLinear SOLver). An absolute and relative tolerance value was set to 105. The separation was undertaken throughout 28 cycles. During the operation, samples of extract and raffinate average concentrations were withdrawn (referent to a complete cycle, namely: cycle 2; 4; 6; 8; 10; 13; 15; 17; 19; 27), To plot the FlexSMB-LSRE concentration profile, from cycle 20 to cycle 25, a single sample in each cycle was withdrawn for 10 seconds, at the middle of the switching time period , by means of a 6 ports sampling valve installed on the outlet of column 6 for internal profile sample I, III, IV and V; and at the extract and raffinate ports for profiles samples VI and II, respectively, see Annex VIII. The same procedure was then repeated in cycle 27, but now with all sampling apparatus occurring within the same cycle. Both sampling procedures resulted in almost the same concentration profile, proving that collecting six samples per cycle will not influence too much the SMB internal profiles. In Figure 6.21 the internal concentration profile obtained from cycle 20 to 27.. The simulated results fit well the experimental ones, even the secondary plateau noted next to the left of major plateau of the more retained species in section II and the right of the major plateau of the less retained species in section III (related with dead volumes of both extract and raffinate lines), are well predicted by the extended dead volumes model used. All samples (extract and raffinate average concentrations, as well as internal profiles) were loaded into a 10l loop and then injected by means of a Knauer injection valve installed on a Gilson HPLC unit into an analytical column CHIRALCEL OBH (25cm and 0.46cm I.D., supplied by Chiral Technologies, France) using as mobile phase the same solution used for eluent purposes. The consequent peaks were measured by means of a UV detector set at 270nm and concentrations determined according with calibration curve obtained from linear regression of Area vs. Concentration ( of 5 standards (g.dm-3, of each enantiomer) with a with a All experiments (separation with the SMB unit and analytical procedures) were run at laboratorial conditions (approximately 25C). 4.3. Control of SMB units In recent years the control of SMB units has also been wide investigated (Erdem et al., 2004b; Engell, 2007; Grossmann et al., 2008a; Grossmann et al., 2008b). Several reports on dynamic control strategies include nonlinear control strategies such as: the input-output linearizing control, where the controller action is based on a nonlinear state estimator using the TMB model (Kloppenburg and Gilles, 1999a); and model predictive control (MPC) (Natarajan and Lee, 2000; Erdem et al., 2004a; Dietz and Corriou, 2008); or design on the basis of neural networks (Wang et al., 2003). Also a model based SMB control where an optimal trajectory is calculated off-line was proposed by (Klatt et al., 2000; Klatt et al., 2002) and from wave reconstruction (Kleinert and Lunze, 2008). A more recent strategy based on the nonlinear wave propagation phenomena aims to control the central sections of the SMB unit by controlling the position of the concentration fronts (Schramm et al., 2003a). The control o f chromatographic processes (SMB included) by means of the standard control procedures (P, PI or PID controllers), but detecting characteristic points of the unit where the history of a specific variable of the fractions of the mixture to be separated will be representative for the control action was also addressed (Valery and Morey, 2009). 5. Conclusions

Tuesday, May 19, 2020

The Role Of Federalism And Its Effect On American Government

nt’s activities Federalism is known to be when national government shares power with multiple lower governments and they exercise power over the same people or same territory. Federalism has impacted and continues to impact American government and was created to help groups keep and remain their same powers although time changes. Unlike the unitary system where the lower levels of government have little independent power, the system of federalism has separate powers for lower levels of government and can exercise it freely. According to the Tenth Amendment: â€Å"The powers not delegated to the United States by the Constitution, nor prohibited by it to the States are reserved to the States respectively, or to the people.† The U.S Constitution divides power between federal and state Governments. This means that the power is separated between federal, state, and local governments each having their own primary roles. Much like checks and balances these governments have certain power that allows each not to obtain too much power. To starts off, the states have very significant powers including police ad concurrent powers. A given state has the ability to develop and enforce criminal codes, administer health and safety rules, and regulate marriage and divorce laws. States also regulate individual livelihoods (through licenses to practice medicine, law, and various other professions), and define and enforce laws concerning private property. The states and the federal government alsoShow MoreRelatedThe New Deal and American Federalism885 Words   |  4 Pages Federalism may be described as a system of government that features a separation of powers and functions between the state and national governments. This system has been used since the very founding of the United States. The constitution defines a system of dual federalism, which ensures sovereignty of the state and national governments. 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The Yellow Wallpaper, By Charlotte Perkins Stetson

â€Å"The Yellow Wallpaper†, written by Charlotte Perkins Stetson, is a first person narrative told by a depressed wife, who wrote ten short entries in a secret journal. In the narrative, the wife’s physician and husband diagnose her with â€Å"temporary nervous depression† (Stetson 648). The narrative took place in the 1900’s when there were minimal treatments to cure nervous depression. The husband was a dominant physician in the story who believed that bed rest and the minimum amount of daily activity would cure the wife’s state of depression. The failed treatments to cure what was assumed to be â€Å"nervous depression† later caused the wife to lose her sanity, emotional stability, and mental focus toward the end of the story. There are a plethora of different depression stages whose symptoms match the wife’s, but the closest type of depression associated with her symptoms would be postpartum depression and postpartum psychosis. I f not treated correctly, postpartum depression can lead to a more severe type of depression called postpartum psychosis, which causes the patient to have suicidal tendencies and mass hallucination. In researching depression after birth, one may prove that the wife suffered from postpartum depression, which leads to post partum psychosis; this explains her symptoms and loss of sanity throughout the narrative; specialists in the field of after birth depression support this statement. To comprehend postpartum depression and postpartum psychosis, an individualShow MoreRelatedThe Yellow Wallpaper By Charlotte Perkins Stetson Essay2509 Words   |  11 PagesLENSES The wallpaper in ‘The Yellow Wallpaper’ is symbolic of the gender-based oppression women of the patriarchal time period of its writing, faced; being infantised, not allowed to vote but expected to raise the children and take care of the house. 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The narrator in this article is obviously insane because she thinks everything in the room is for fun, she is abnormally focused on random things, and she does not realize HUGE things like what she is being kept from and how sheRead MoreTaking Risks to Self-fulfillment in The Yellow Wallpaper by Charlotte Perkins Stetso n 959 Words   |  4 Pages To seek a worthwhile life, one must seek self-fulfillment . The female character in The Yellow Wallpaper desires to become more of what she can be in life and breaking free from oppression so she is able to secure the satisfaction of self-fulfillment. In The Yellow Wallpaper, Charlotte Perkins Stetson draws on the idea that self-fulfillment is a desired need, however the means to securing it may not itself be desired. In other words, the cost to secure self-fulfillment may be arduous andRead More The Yellow Wallpaper898 Words   |  4 Pages Charlotte Perkins Gilman was born in Hartford, Connecticut on July 3, 1860. 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Wednesday, May 6, 2020

Evolution of Aesthetic Medicine and its Implications on...

Throughout this century, the term natural beauty has taken a wide variety of definitions. Aesthetic treatments are rapidly becoming socially sought after in large urbanized communities, and this craze is rapidly progressing towards a flawless sales tactic for all cosmetic surgeons and media alike—proclaiming that one should invest in themselves. What was once seen as treatment for individuals in dire need is now evolving into a marketable service rendered to those with the means to obtain it. It is clear that demand for aesthetic surgery has skyrocketed in recent years, an increase caused by modern marketing tactics, technological development, as well as the modern idea of individualism and self-expression through artificial body†¦show more content†¦One patient was satisfied with the results, but the other was unsure she wanted to undergo the procedure in the first place. This falls into the human understanding of using stereotypes in order to organize social worlds (Anonymous 2008). Some individuals still have a clouded perception on their motives for undergoing such procedures, and it is not until the damage has been done that feelings of regret occur. Media has created a massive social cult for several years by creating what is seen as the ideal physique, encouraging astray individuals to take extreme measures in order to conform. Another significant factor towards the recent increase of cosmetic surgery procedures is attributed to major technological advancements in recent years. Modern advances in technology have significantly decreased pain level as well as post-operation complications. Cosmetic surgeons are also widely available and offer competitive rates in many urban centers. The repackaging of cosmetic surgery as a business has also allowed for surgeons to advertise, which only adds to a consumer’s temptation. This allows clinics to offer financing and other methods of payment, significantly increasing the accessibility to such services. 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Analysis Of Trifles By Susan Glaspell - 804 Words

In the play Trifles, Susan Glaspell creates a situation that at first glance appears to place a woman at fault, but as the readers continue, he/she realizes that the truth is the opposite to what it appears to be. It is interesting to see how the author uses the image of a perfect husband to portray irony with the hidden theme of isolation and patriarchy within their domestic relationship. This irony leads into Minnie Foster, also called Mrs. Wright, to use the idea of justice vs. law within this tragi-comedy. Minnie Foster used to be a happy, young girl who use to sing in a choir. She met a farmer, with a reputation for being a good, responsible, hardworking man, named John Wrights, who later became her husband. After their marriage, her†¦show more content†¦His wife does nothing about his actions to protect his reputation, which gives him more pride and power in his wrong acts. Female identity was obviously not respected within Mr. and Mrs. Wright’s marriage. In this case, Mr. Wright just completely forbade her from doing anything. Mr. Wright takes away his wife’s dignity, leading her to feel fed up and seek for her justice. Different forms of solidarity were portrayed by both genders in this tragic comedy. While Mrs. Wright was imprisoned for being found as the main suspect in the criminal investigation, all men in her case just followed the law, not willing on understanding why she committed this murder. Mrs. Wright had a pet canary. This was the only spirit and hope; they both loved to sing and that was the only thing that gave her happiness. She was trapped unhappily in her marriage just as the bird was when it was caged. Mr. Wright killed his wife’s canary, like always not caring about her interests. Now, that he destroyed the only two things that loved: singing, and her bird, Mrs. Wright revolted by destroying his life just how he did to herself. Mrs. Peter and Mrs. Hale were the only ones who understood why she committed this murder against her husband and forgave her for it because they believed she was justified. Therefore, they did right by going against the law. Mrs. Hale and Mrs. Peter saved her fromShow MoreRelatedScript Analysis of Trifles by Susan Glaspell910 Words   |  4 PagesScript Analysis of â€Å"Trifles† by Susan Glaspell Summary   In the play Trifles by Susan Glaspell, there are five characters, three men and two women.   They are in a house where the murder of Mr. Wright took place the day before.   The men are trying to find evidence to name a killer or motivation to name Mrs. Wright as the murderer.   While the men are downstairs, the women occupy themselves with looking around the kitchen and living room.   They take note of Mrs. Wrights canned fruit and the factRead MoreAnalysis Of Trifles By Susan Glaspell846 Words   |  4 PagesSociety has put abnormal standards between women and men. 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While the men are trying to solve the crime their wivesRead MoreAnalysis Of Trifles By Susan Glaspell1255 Words   |  6 PagesMurder, torture, and mayhem are merely three of the unique problems that can be found throughout the one act play Trifles by Susan Glaspell. The writer opens up the story by explaining the situation of Mrs. Wright, a middle aged woman who is being accused of murdering her husband. The crime scene is a mess. A sheriff, the prosecuting attorney and their wives are looking in to the gruesome death that occurred upstairs in the Wright household. It is immediately found that the men focus their attentionRead MoreAnalysis Of Trifles By Susan Glaspell1829 Words   |  8 PagesMurder, torture, and mayhem are merely three of the unique problems that can be found throughout the one act play Trifles by Susan Glaspell. The writer opens up the story by explaining the situation of Mrs. Wright, a middle aged woman who is being accused of murdering her husband. The crime scene is a mess. A sheriff, the prosecuting attorney and their wives are looking in to the gruesome death that occurred upstairs in the Wright household. It is immediately found that the men focus their attentionRead MoreAnalysis Of Trifles By Susan Glaspell1042 Words   |  5 Pagesits underlying meaning can represent to each character individually and together. In the short play â €Å"Trifles† by Susan Glaspell, readers and viewers are taken back to a period that is a lot different than the current. From the surroundings, viewpoints of each sex and their assigned roles in the society all gave a greater understanding of what was portrayed and how it was essentially handled. Trifles started with the Sheriff and his wife Mrs. Peters, Mr. Hale and Mrs. Hale and the County Attorney enteringRead MoreTrifles By Susan Glaspell Analysis1738 Words   |  7 Pageswomen dont realize the struggle women before them had to undergo. In the late 19th century women werent important, respected, or anywhere near equal to men. It was common for women to be misunderstood and or assumed by men to be uncivil. Trifles by Susan Glaspell shows the depiction of women towards the end of the 1800s. Men werent as kind or laid back when it came to running the household and handling every day matters as a family. Men were dominant. It was the patriarchal ignorance of the lateRead Mor eTrifles By Susan Glaspell Analysis1257 Words   |  6 PagesTrifles by Susan Glaspell is a tragic mysterious drama that has to deal with a murderous wife, and a couple of friends who cover up her tracks. Throughout the story Glaspell gives clues to the reader to help him or her figure out what will happen in the end. Glaspell Wrote Trifles in 1916, according to the year it is safe to assume that this mysterious short story was placed in a time around the 1910’s setting. 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Role and Function of Rbi free essay sample

Assignment No 1 Role and Function of RBI Introduction:- Reserve bank of India (RBI) is nation’s central bank. RBI began operation since 1935, and stood at the centre of India’s financial system, with a fundamental commitment to maintaining the nation’s monetary and financial stability. From ensuring stability of interest and exchange rates to providing liquidity and an adequate supply of currency and credit for the real sector; from ensuring bank penetration and safety of depositors’ funds to promoting and developing financial institutions and markets, the Reserve Bank plays a crucial role in the economy. Our decisions touch the daily life of all Indians and help chart the country’s current and future economic and financial course. Over the years, our specific roles and functions have evolved. However, there have been certain constants, such as the integrity and professionalism with which the Reserve Bank discharges its mandate. Organization Structure:- Central Board of Directors by the Numbers Official Directors 1 Governor 4 Deputy Governors, at a maximum Non-Official Directors directors—nominated by the Central Government to represent each local board 10 directors nominated by the Central Government with expertise in various segments of the economy. We will write a custom essay sample on Role and Function of Rbi or any similar topic specifically for you Do Not WasteYour Time HIRE WRITER Only 13.90 / page 1 representative of the Central Government 6 meetings—at a minimum—each year 1 meeting—at a minimum—each quarter Below diagram shows the current structure of the Reserve Bank of India (RBI). Central office departments:- Over the last 75 years, as the functions of the Reserve Bank kept evolving, the work areas were allocated among various departments. At times, the changing role of the Reserve Bank necessitated closing down of some departments and creation of new departments. Currently, the Bank’s Central Office, located at Mumbai, has twenty-seven departments. These departments frame policies in their respective work areas. They are headed by senior officers in the rank of Chief General Manager. Markets Department of External Investments and Operations

Music Essay Thesis Example For Students

Music Essay Thesis Music has always been a voice for the ages. It is one universal language that we all speak. Most people use it to express what they are feeling, some people use it to relate to, everyone enjoys it in one way or another. Thats where my point comes in; there is no doubt that music has changed according to the changes in society. My generations music censorship has changed, the way music is conveyed and the lenience of the music has allowed for the stories being told through the music to change and the depth of the music and the implications of the music to diversify . Music today is a genuine combination of yesterdays music with an original spin. This hat makes our music worth listening to. One of the defining changes would be that a large percentage of students ages fourteen through seventeen say that Rap and Hip/ Hop are the kind of music they listen to due to its sudden popularity and admiration of mainstream music. Not only that but, it has broken barriers for censorship in Rap music. Rap music has had little impact from the use of censorship because the artists have not yet been impaired by it. The need for cleaner rap music has arisen ND left a very small dent in the rap world. The degrading words and phrases and the explicit language may or may not stay within the culture of rap music may change to fill the need for cleaner music, but for now rap is still rap. (Helium. Com/Cody Kibble-Author/How Censorship Has Changed Rap Music). Rap and Hip/Hop music will always be controversial because of the paths these artists have walked. The stories being told and the emotional ride listeners are taken on are supposed to be raw first- hand accounts of these rappers and artists lives. To put a censorship on the truth is unsustainable since the truth always comes out.. Mine has been under scrutiny for his vulgar language and graphic stories being expressed in his songs since the beginning of his mega stardom. The fact of the matter is that he has a huge fan base with a diverse age group and it makes parents everywhere cringe. Censorship was born on parental concern . Many people believe rap is too graphic with a lot of unnecessary profanity. Parts of society will go far as to say that these rappers and artists are abusing their rights. There was once something called Common Decency that has disappeared. I think that those persons who may lack common decency have found a perfect shield to hide behind and they call it Freedom of Speech. (Helium. Com/Peggy Mallory-Author/Censorship in the Music Industry in the U. S. ). Although Freedom of Speech does provide the perfect shield for rap artists to hide behind, I also think that it serves as the perfect defense. The ver y definition of freedom is the power to determine action without restraint. This amendment was formed to let the people freely express their beliefs, ideas, and stories. The fact that censorship in rap music has changed as much as it has allows for different estimation to be shared and different walks of life to be exposed to the fans. Furthermore, people everywhere are starting to realize Just that. In fifty years music has gone from do-whoppers with nerdy glasses and suits, to artists of today having almost complete freedom of expression. (Helium. Com/David Thatches-Author/How American Music Has Changed Over the Last Fifty Years. This broadened our insights on the struggles the members of our community and generation go through all the Music Essay By wantons amounts of people who disagree with what rap music has to say. The truth isnt always pleasant though, and neither is all Rap Music. Music is the binding agent and bridge to the feelings that are unclear. It seems to be too good to be true that were able to use music as a tool. Theres something about a voice thats personal, not unlike the particular odor or shape of a given human body. .u6d25af94256be806b2645ed135bc5c74 , .u6d25af94256be806b2645ed135bc5c74 .postImageUrl , .u6d25af94256be806b2645ed135bc5c74 .centered-text-area { min-height: 80px; position: relative; } .u6d25af94256be806b2645ed135bc5c74 , .u6d25af94256be806b2645ed135bc5c74:hover , .u6d25af94256be806b2645ed135bc5c74:visited , .u6d25af94256be806b2645ed135bc5c74:active { border:0!important; } .u6d25af94256be806b2645ed135bc5c74 .clearfix:after { content: ""; display: table; clear: both; } .u6d25af94256be806b2645ed135bc5c74 { display: block; transition: background-color 250ms; webkit-transition: background-color 250ms; width: 100%; opacity: 1; transition: opacity 250ms; webkit-transition: opacity 250ms; background-color: #95A5A6; } .u6d25af94256be806b2645ed135bc5c74:active , .u6d25af94256be806b2645ed135bc5c74:hover { opacity: 1; transition: opacity 250ms; webkit-transition: opacity 250ms; background-color: #2C3E50; } .u6d25af94256be806b2645ed135bc5c74 .centered-text-area { width: 100%; position: relative ; } .u6d25af94256be806b2645ed135bc5c74 .ctaText { border-bottom: 0 solid #fff; color: #2980B9; font-size: 16px; font-weight: bold; margin: 0; padding: 0; text-decoration: underline; } .u6d25af94256be806b2645ed135bc5c74 .postTitle { color: #FFFFFF; font-size: 16px; font-weight: 600; margin: 0; padding: 0; width: 100%; } .u6d25af94256be806b2645ed135bc5c74 .ctaButton { background-color: #7F8C8D!important; color: #2980B9; border: none; border-radius: 3px; box-shadow: none; font-size: 14px; font-weight: bold; line-height: 26px; moz-border-radius: 3px; text-align: center; text-decoration: none; text-shadow: none; width: 80px; min-height: 80px; background: url(https://artscolumbia.org/wp-content/plugins/intelly-related-posts/assets/images/simple-arrow.png)no-repeat; position: absolute; right: 0; top: 0; } .u6d25af94256be806b2645ed135bc5c74:hover .ctaButton { background-color: #34495E!important; } .u6d25af94256be806b2645ed135bc5c74 .centered-text { display: table; height: 80px; padding-left : 18px; top: 0; } .u6d25af94256be806b2645ed135bc5c74 .u6d25af94256be806b2645ed135bc5c74-content { display: table-cell; margin: 0; padding: 0; padding-right: 108px; position: relative; vertical-align: middle; width: 100%; } .u6d25af94256be806b2645ed135bc5c74:after { content: ""; display: block; clear: both; } READ: Music and Teenagers EssaySummoned through the belly, hammered into form by the throat, given propulsion by bellows of lungs, teased into final form by tongue and lips, a vocal is a kind of audible kiss, a blurted confession, a soul-burp you really cant keep from issuing as you make your way wrought the material world (Expert from Jonathan Lathes intro to the Greatest Singers of All Time featured in the November 27,2008 issue of Rolling Stone Magazine). Music deciphers confused moods and feelings, the different genres attribute to feelings, thoughts, and moods for those next three minutes and twenty- six seconds. Music today has gone from stories about fun and problem-free tunes to the seedy underbelly that has always existed in our society that is now being made into realistic renditions of what Americas youth is going through. For the music rises from a generation that feels with some Justice that they have been betrayed by those who came before them, that they are best tolerated in schools, feared on the streets, and almost inevitably destined for the hellholes of prison. They grew up hated, hungry, and unloved. And this is the psychic fuel that seems to generate the anger that seems endemic in much of music and property. (Treacherousness. Com/Miami ABA Kamala-Activist). Miami ABA Kamala has had his share of life stories. With a history of activism, radio Journalism, and even being an involved member of the Black Panthers. Whether it be a life of brutality and mistreatment or the way love and life can change someone forever. Everyone is either a disheveled soul with an intense personal his tory and a story to tell or someone Just wanting a good beat and fun rhythm to dance to Most underground rappers and mainstream rappers, if theyre lucky, can relate to what Miami ABA Kamala had to say. It is easy to talk down on mainstream music because it is shallow bubble gum-pop that takes little to no brain power to comprehend. Many of the critics of this very topic chose to ignore this. What strikes me odd is that when people talk about modern day music is their refusal to take historical context, and the evolving economics of the music industry into account. (Helium. Com/Tom Windward- Author/Search For the Meaning of Modern Day Music). A lot of todays music is altered to the specifications of the industry in order to make money. Music that we hear on the radio and see on television is what is known as mainstream. The industry does this ultimately to sell the artist. The music played is made to speak to the masses, which, in turn, means it is easy to understand. It is human condition and a common human endeavor to make music deep and to make music shallow. There is no predominance of shallow music. It is Just that the shallow stuff is easier for the profit makes to broadcast more often and it is easier to incorporate and remember. (Helium. Come Elizabeth M. Young-Author/ Music is Losing Its Depth). This is a key point in this argument. My generations music is Judged by the mainstream artists when there is so much more going on. Maybe though, the gems in the rough are better off left there. Most of the time, artists are changed into a ND more teen and pop idols out of the Indies scene and into the big times, which unfortunately, created a loss in depth in the music itself but a significant increase in profit. (Helium. Com/Cayman Persisting -Author/Music is Losing Its Depth). The wonderful truth of the music and youth demographic is that there are different genres. Conclusively meaning, a different fan base. A band by the name of Uniform and Sons has made the Billboards Top 100 List recently, and they couldnt be further from artists like Eke$ha, Wiz Kalmia, and Kathy Perry, Since they formed in December 007, the members of Uniform ; Sons have shared a common purpose: to make music that matters, without taking themselves too seriously. Four young men from West London in their early twenties, they have fire in their bellies, romance in their hearts, and rapture in their masterful, melancholy voices. (mummifications. Com). This band is living proof that, in order to be successful, you do not have to be on the conveyor belt that seemingly is the music industry today. Their lyrics are easy to empathic and it is rendered differently from a lot of the other artists on the charts today. The need for the constant change in our environment, has shortened our attention span to the point that learning anything in depth, is a struggle that only the most de termined learner would undertake. (Helium. Mom/Steve Burden-Author/Music is Losing Its Depth). Music does not have to be a challenge to understand. Even though, the more obscure bands could be considered weird, what matters is that theyre there. It is able to balance out the bubble gum pop and the original music that my generation still has to offer. The music the youth of today is listening to and making is an infusion of music from sat generations and rhythms and sounds of this generation. The difference between yesterday and today are the stories. .u9a5f13d6b5c537144732ce981a52897e , .u9a5f13d6b5c537144732ce981a52897e .postImageUrl , .u9a5f13d6b5c537144732ce981a52897e .centered-text-area { min-height: 80px; position: relative; } .u9a5f13d6b5c537144732ce981a52897e , .u9a5f13d6b5c537144732ce981a52897e:hover , .u9a5f13d6b5c537144732ce981a52897e:visited , .u9a5f13d6b5c537144732ce981a52897e:active { border:0!important; } .u9a5f13d6b5c537144732ce981a52897e .clearfix:after { content: ""; display: table; clear: both; } .u9a5f13d6b5c537144732ce981a52897e { display: block; transition: background-color 250ms; webkit-transition: background-color 250ms; width: 100%; opacity: 1; transition: opacity 250ms; webkit-transition: opacity 250ms; background-color: #95A5A6; } .u9a5f13d6b5c537144732ce981a52897e:active , .u9a5f13d6b5c537144732ce981a52897e:hover { opacity: 1; transition: opacity 250ms; webkit-transition: opacity 250ms; background-color: #2C3E50; } .u9a5f13d6b5c537144732ce981a52897e .centered-text-area { width: 100%; position: relative ; } .u9a5f13d6b5c537144732ce981a52897e .ctaText { border-bottom: 0 solid #fff; color: #2980B9; font-size: 16px; font-weight: bold; margin: 0; padding: 0; text-decoration: underline; } .u9a5f13d6b5c537144732ce981a52897e .postTitle { color: #FFFFFF; font-size: 16px; font-weight: 600; margin: 0; padding: 0; width: 100%; } .u9a5f13d6b5c537144732ce981a52897e .ctaButton { background-color: #7F8C8D!important; color: #2980B9; border: none; border-radius: 3px; box-shadow: none; font-size: 14px; font-weight: bold; line-height: 26px; moz-border-radius: 3px; text-align: center; text-decoration: none; text-shadow: none; width: 80px; min-height: 80px; background: url(https://artscolumbia.org/wp-content/plugins/intelly-related-posts/assets/images/simple-arrow.png)no-repeat; position: absolute; right: 0; top: 0; } .u9a5f13d6b5c537144732ce981a52897e:hover .ctaButton { background-color: #34495E!important; } .u9a5f13d6b5c537144732ce981a52897e .centered-text { display: table; height: 80px; padding-left : 18px; top: 0; } .u9a5f13d6b5c537144732ce981a52897e .u9a5f13d6b5c537144732ce981a52897e-content { display: table-cell; margin: 0; padding: 0; padding-right: 108px; position: relative; vertical-align: middle; width: 100%; } .u9a5f13d6b5c537144732ce981a52897e:after { content: ""; display: block; clear: both; } READ: Bob Marley EssayThe stories have changed because censorship is more complaisant with the lyrics and has taken note that the truth is powerful and to bind expression with such boundaries would limit the voice of the people. The depth and meaning are a result of smudging the line that is censorship and the overall message being exposed to fans of all kinds of bands and artists has altered to where music can be more about real life testimonies and insights to different lifestyles than partying and having a good time.