Recovery particle extraction

The slurry process is the oldest and still widely used method for manufacturing polymers of ethylene, propylene and higher a-olefins. In this process, the monomer dissolves in the polymerisation medium (hydrocarbon diluent) and forms a solid polymer as a suspension containing ca 40 wt-% of the polymer the polymerisation occurs below the melting point of the polymer. In slurry polymerisation, the temperature ranges from 70 to 90 °C, with the ethylene pressure varying between 7 and 30 atm. The polymerisation time is 1-4 h and the polymer yield is 95-98 %. The polymer is obtained in the form of fine particles in the diluent and can be separated by filtration. Removal of the catalyst residues from the polymer can be achieved by the addition of alcohol (isopropanol, methanol), followed by recovery and extraction of the catalyst residues. The polymer is freed from diluent by centrifuging and then dried. In the case of polypropylene manufacture, the atactic fraction remains in the diluent [28,37]. 

Including the transferred particles of the interfacial layer (IL), a recovery of extracted magnetite particles of 76 % as limit value could be achieved (dashed line in Fig. 20b). 

Another example is the purification of a P-lactam antibiotic, where process-scale reversed-phase separations began to be used around 1983 when suitable, high pressure process-scale equipment became available. A reversed-phase microparticulate (55—105 p.m particle size) C g siUca column, with a mobile phase of aqueous methanol having 0.1 Af ammonium phosphate at pH 5.3, was able to fractionate out impurities not readily removed by hquid—hquid extraction (37). Optimization of the separation resulted in recovery of product at 93% purity and 95% yield. This type of separation differs markedly from protein purification in feed concentration ( i 50 200 g/L for cefonicid vs 1 to 10 g/L for protein), molecular weight of impurities (<5000 compared to 10,000—100,000 for proteins), and throughputs ( i l-2 mg/(g stationary phasemin) compared to 0.01—0.1 mg/(gmin) for proteins). 

However, the quantity of Pa produced in this manner is much less than the amount (more than 100 g) that has been isolated from the natural source. The methods for the recovery of protactinium include coprecipitation, solvent extraction, ion exchange, and volatility procedures. AH of these, however, are rendered difficult by the extreme tendency of protactinium(V) to form polymeric coUoidal particles composed of ionic species. These caimot be removed from aqueous media by solvent extraction losses may occur by adsorption to containers and protactinium may be adsorbed by any precipitate present. 

Albertsson (Paiiition of Cell Paiiicle.s and Macromolecules, 3d ed., Wiley, New York, 1986) has extensively used particle distribution to fractionate mixtures of biological products. In order to demonstrate the versatility of particle distribution, he has cited the example shown in Table 22-14. The feed mixture consisted of polystyrene particles, red blood cells, starch, and cellulose. Liquid-liquid particle distribution has also been studied by using mineral-matter particles (average diameter = 5.5 Im) extracted from a coal liquid as the solid in a xylene-water system [Prudich and Heniy, Am. Inst. Chem. Eng. J., 24(5), 788 (1978)]. By using surface-active agents in order to enhance the water wettability of the solid particles, recoveries of better than 95 percent of the particles to the water phase were obsei ved. All particles remained in the xylene when no surfactant was added. 

Fluidised beds have been used previously for the industrial-scale recovery of the antibiotics streptomycin and novobiocin.30 However, more recently, considerable interest has been shown in the use of fluidised beds for the direct extraction of proteins from whole fermentation broths.31 In a packed bed, the adsorbent particles are packed within the contactor. The voidage, that is, the inter-particle space, is minimal and thus feedstock clarification is mandatory to avoid clogging of the bed. In a fluidised/expanded bed, the adsorbent bed is allowed to expand by irrigation with feedstock. Bed voidage is increased, allowing the passage of particulates in the feed. The diameters of the adsorbent beads are exaggerated for illustrative clarity. 

The separation of solids from liquids forms an important part of almost all front-end and back-end operations in hydrometallurgy. This is due to several reasons, including removal of the gangue or unleached fraction from the leached liquor the need for clarified liquors for ion exchange, solvent extraction, precipitation or other appropriate processing and the post-precipitation or post-crystallization recovery of valuable solids. Solid-liquid separation is influenced by many factors such as the concentration of the suspended solids the particle size distribution the composition the strength and clarity of the leach liquor and the methods of precipitation used. Some important points of the common methods of solid-liquid separation have been dealt with in Chapter 2. 

To obtain representative samples from nonhomoge-neous sample materials, such as polymer compounds, particle-size reduction techniques need often to be applied (not for film) [50]. Also, for destructive inpolymer additive analysis it is advantageous to change the physical state of solid samples to provide a larger surface area per unit mass. Complete extraction is sometimes achieved only after grinding the sample. Typically, Perlstein [51] has reported recoveries of only 59 % for extraction of Tinuvin 320 from unground PVC after 16 h of Soxhlet extraction with diethyl ether while recoveries rise to 97 % for ground polymer. 

The extraction time has been observed to vary linearly with polymer density and decreases with smaller particle size [78,79]. The extraction time varies considerably for different solvents and additives. Small particle sizes are often essential to complete the extraction in reasonable times, and the solvents must be carefully selected to swell the polymer to dissolve the additives quantitatively. By powdering PP to 50 mesh size, 98 % extraction of BHT can be achieved by shaking at room temperature for 30 min with carbon disulfide. With isooctane the same recovery requires 125 min Santonox is extractable quantitatively with iso-octane only after 2000mm. The choice of solvent significantly influences the duration of the extraction. For example talc filled PP can be extracted in 72 h with chloroform, but needs only 24 h with THF [80]. pH plays a role in extracting weakly acidic and basic organic solutes, but is rarely addressed explicitly as a parameter. 

Principles and Characteristics Supercritical fluid extraction uses the principles of traditional LSE. Recently SFE has become a much studied means of analytical sample preparation, particularly for the removal of analytes of interest from solid matrices prior to chromatography. SFE has also been evaluated for its potential for extraction of in-polymer additives. In SFE three interrelated factors, solubility, diffusion and matrix, influence recovery. For successful extraction, the solute must be sufficiently soluble in the SCF. The timescale for diffusion/transport depends on the shape and dimensions of the matrix particles. Mass transfer from the polymer surface to the SCF extractant is very fast because of the high diffusivity in SCFs and the layer of stagnant SCF around the solid particles is very thin. Therefore, the rate-limiting step in SFE is either... 

As diffusion to the surface of a polymer is one of the limiting steps in extraction, the particle size or film thickness of a sample is also important [278,333,337-340]. With the typical diffusion coefficients of additives in polymers a particle diameter of about 0.3 mm is required for an extraction time of about 1000 s at 40 °C. An exception to this is the extraction of thin films and foams, for which the shortest dimension is small. It is not surprising that no more than 50 % of antioxidants could be extracted from PP pellets as opposed to 90 % recoveries from the same polymer extruded into film [341]. Grinding of the polymer is usually an essential step before extraction. Care should be taken to avoid loss of volatile additives owing to the heat generated in such processes. Therefore, cryogrind-ing is preferred. 

On-line SFE-SFC method development for validated quantitative analysis of PP/(Irganox 1010/1076, Tinuvin 327) has been reported [93]. SFE conditions required optimisation of extraction time and pressure, matrix type (particle or film) and matrix parameters (particle size, film thickness, sample weight). About 30% of extracts were lost during collection. Very poor recoveries (20-25 %) were reported from ground samples (particle size 100 p,m dependent recoveries of 45-70% for 30-p.m-thick films. Biicherl... 

Supercritical fluid extraction (SFE), microwave-assisted extraction (MAE) and Soxhlet extraction under various experimental conditions were applied for spiked poly(vinyl) chloride samples. Extracted dyes were separated in an ODS column (250 X 4.6 mm i.d. particle size 5 jum) using methanol as the mobile phase. Dyes are well separated by this method as demonstrated in Fig. 3.59. The optimal parameters of the extraction methods are compiled in Table 3.23. Recoveries depended on both the type of extraction method and the chemical structure of the dye. It was found that the highest recovery can be obtained by MAE and the extraction efficacy was the lowest for Solvent red 24 [129],... 

Separation of amines was realized in an ODS column (250 x 3 mm i.d. particle size 5 /tm) at 30°C. The flow rate was 0.3 ml/min and amines were detected at 280 nm. Solvents A and B for gradient elution were ACN and 3 mM phosphate buffer (pH = 7). The gradient started with 15 per cent A for 2 min then to 60 per cent A in 50 min. Chromatograms illustrating the separation of amines are shown in Fig. 3.72. It was established that the recoveries of both SFE and MAE were higher than those of traditional solvent extraction, therefore, their application for the analysis of carcinogenic aromatic amines in leather is highly advocated [140],... 

Recently, three papers have reported the determination of risperidone and its active metabolite 9-hydroxyrisperidone using LLE and SPE technologies. The analytical columns used to separate these compounds were C4 or C18 bonded phases of 3 pm or 5 pm particle sizes with UV/VIS detection. Mobile phases consisted of phosphate bufiers (pH 3-4) in acetonitrile. The sample volumes used ranged from 200 pi to 1 ml, with extraction recoveries averaging 90%. The limits of quantitation ranged from 0.5 to 10 ng/ml in human plasma (Nagasaki et al., 1999 Avenso et al., 2000 Titier et al., 2002). A study by Titier showed the simultaneous determination of clozapine, olanzapine, haloperidol, risperidone, and its active metabolites by RP-HPLC in human plasma. The assay involved LLE with a hexane/isoamyl alcohol mixture... 

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