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Specialty Chemicals
Chemical Products
Chemical Products can be conveniently separated into three categories (according to Cussler and Moggridge)
- Micro- and macrostructured products - Specialty chemicals - Devices for chemical changes
Specialty Chemicals
- The design of a specialty chemical usually starts with a known reaction - The design process involves then first the verification of the synthesis - The second design step is then to develop the reaction engineering needed - Separation techniques in relation to the involved costs are a key element of specialty chemical design
In most cases, he will not initially get results that are as good as the chemist's, a result of the chemist's greater skill and of the inadvertent omission of nuances of chemical technique. But eventually, he should equal or surpass the chemist's laboratory results. He is then ready for the reaction engineering.
Reaction Engineering
We have duplicated the chemist's results We now need to consider the speed and the selectivity of the chemical reaction.
The chemist has shown that this synthetic route is possible. We need to discover how much it can make
Reaction Engineering
Determining the rate-limiting step is detailed in texts on chemical kinetics!
- Normally, we will want to know the effect of changing the concentration of the limiting reagent (in order to determine the order of the reaction) - We then measure how the rate changes with temperature and with stirring.
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Remove the most plentiful products early Do the hardest separations last Remove any hazardous materials early
These three heuristics (also often given for commodity chemical separation!), are best understood by imagining the sorting of tableware removed from a big dishwasher:
- We separate the sharp knives first because they can cut us; they are a potential hazard. - We sort the forks and spoons early, because there are a lot of each and because the separation is easy. - We separate Aunt Evetta's spoons last because they look similar to some of the other spoons.
However, the caution that we remove these added species quickly is the real message of the heuristic. These added species will be much harder to remove the more we close onto the final product.
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Fractional distillation is usually not important for speciality chemicals because these tend to have low volatility and to be thermally unstable. (However, it is the most important separation process for commodity chemicals. This process is basic to the estimated 40,000 columns that consume about 6% of the energy used in the USA!). Fractional distillation will be important to many peripheral steps in specialty manufacture, including the recycle and reuse of solvents. One method of distillation that is quite common for specialty chemicals is steam distillation
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Steam Destillation
In this method a temperature-sensitive organic that is only partially miscible in water is distilled from a two-phase liquid mixture. The presence of the aqueous rich phase lowers the boiling point and allows distillation of the organic phase (with a high boiling point) without its decomposition. Steam distillation is the most common method of obtaining extracts from plants. The vapour pressure for two liquids can be approximated as:
(two-phase system)
Because the boiling point is the temperature at which the total vapor pressure equals the external applied pressure, this implies that the boiling point of the two-phase mixture is lower than both the boiling points of the individual components.
Thus even relatively nonvolatile species can be steam distilled at a temperature lower than the boiling point of water. Moreover, once the distillate is condensed, the two liquids separate out again and so the removal of the added water is easy.
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Extraction
In extraction, we begin with the dilute solution containing the specialty product produced by our batch reactor. We contact the solution with samples of solvent in which the product is more soluble (we thus concentrate the product, not necessarily selectively). If the relative solubility (the solubility of the product in the original solution relative to that in the extraction solvent) is small, then that solvent (extractant) is a good choice For the product 1 in equilibrium between solvent and feed we have
Extraction
To identify m we recognize that for saturation in the feed and solution we have
In order to seek for efficient extraction we should look for low relative solubility
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Extraction
The second key to extraction is to estimate how much separation we can get in a single batch:
Feed volume Feed solute concentration Solvent volume Solvent solute concentration
Combining with the partition coefficient, m, we find the fraction extracted, f, is given by
Again, it should be noted that a small value of m will give a large fraction extracted
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Extraction
Extraction can also be used as a means of purification This commonly makes use of mixer-settlers, consists of one stirred tank, called the mixer, into which both phases are pumped. The resulting emulsion of the feed and solvent phases is then pumped to a second unstirred tank, called the settler, where the two phases are allowed to separate. When used for purification, the mixer-settlers are often arranged in a staged cascade (for simplicity, we assume an aqueous feed and an organic solvent).
Stages 2 and 3 concentrate the product, removing it from the aqueous stream into the organic extract. Stage 1, however, dilutes the product because of washing the feed with the pure solvent. But, although Stage 1 dilutes the product, it also purifies it, preferentially washing away impurities. The price of this purification is dilution.
Adsorption
In adsorption, a feed containing the product is contacted with a solid adsorbent. Because the adsorbent is usually micro-porous, it has a large surface area on which it can adsorb the product. These solute-surface interactions are frequently more selective than the solute-solvent interactions that occur in extraction. Thus adsorption is especially effective for product purification, though it can also be used for product concentration. Like extraction, adsorption is conveniently discussed as three topics:
- how we choose the adsorbent, - how it will work in batch, and - how we will use it to purify the product.
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Adsorption
There are three common classes of adsorbents:
- Carbons have non-polar surfaces that adsorb non-polar solutes. They are manufactured from a variety of sources, including coke, wood, and coconut shells (Carbons made from a mixture of sawdust and pumice are often used to remove color from fine chemical solutions). - Inorganic adsorbents center on activated alumina and silica gels, both of which are used as dessicants. These materials have polar surfaces, and so tend to be more effective for polar solutes. - Synthetic polymers including ion exchangers. Although ion exchangers are most often designed to capture multivalent ions in exchange for monovalent ones, they are often remarkably effective for selectively adsorbing high value-added solutes such as drugs and pigments (Often, the desorption to regenerate the ion exchanger can be more selective than the original adsorption).
Adsorption
The choice of the adsorbent depends on experimental measurements of the equilibrium between product adsorbed versus product in solution. These experimental results, called isotherms, are often presented graphically. Isotherms are often nonlinear, implying that the thermodynamics is more complex than that responsible for the partition coefficient used in extraction.
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Adsorption
Isotherms give the solute volume per volume of adsorbent, q1, as a function of the final solute concentrations in the solution, y1. This means for a batch absorption with a mass balance
where V is the volume of liquid solution and W is the volume of adsorbent, that at equilibrium the solute concentration is lower than the initial feed concentration y10 A simple way to describe the isotherm mathematically is for example the Freundlich isotherm, where K is an equilibrium constant and the exponent n is less than one for a favorable isotherm. In practice such batch adsorptions are uncommon.
One case in which batch adsorption is used concerns the recovery of extracellular products such as antibiotics from a fermentation broth. By dropping the adsorbent directly into the broth, we can adsorb the product directly and avoid the sometimes difficult filtration of the broth.
Adsorption
A more common way to do adsorptions is to put the adsorbent in a packed bed, and to pour the feed solution through the bed. In this way the adsorbent is in equilibrium with the feed concentration and not with the smaller depleted batch concentration (this means that we are higher up the isotherm and the adsorbent adsorbs more). If we feed the product solution into a packed bed, in an ideal case the product will always adsorb until the adsorbent is saturated. This results in a zone of the bed, fully saturated with solute, which grows with time. When the bed is totally saturated, the exiting concentration will jump from zero to the feed concentration ("breakthrough curve)
time when the solute starts to flow out of the bed time when the bed is fully saturated (exhausted)
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Adsorption
Unfortunately, packed beds do not show these ideal step changes in their output. Instead, the concentration profile within the bed is dispersed, caused by
- non-instaneous absorption that is in competition with transport through the bed - inhomogeneities in packing - Taylor dispersion - axial diffusion.
Because the breakthrough is not a step function, we will need to use more adsorbent than the ideal minimum needed. One approximate way to estimate this amount is as a "length of unused bed l'," which can be described as
Adsorption
Interestingly, l' is independent of the length of the bed l This is counterintuitive, as we would expect the concentration profile to spread more the longer the bed and therefore the longer the residence time in the bed is However, most isotherms are favorable; they adsorb more strongly in dilute solution than in concentrated solution (the bent shape of the isotherms) Any solute that strays ahead of the profile is more likely to be adsorbed and thus retarded, and any solute that lags behind tends to flow ahead more quickly. The result is a concentration profile that is self-sharpening and tends to become more like a step function. This tendency of adsorption to correct its own dispersion, makes it one of the key separation processes for specialty products
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Precipitation
Precipitation is triggered by adding a nonsolvent to the solution. The nonsolvent is miscible in the solution, but causes the product to precipitate because its free energy in solution is increased above that of the solid product. Nonsolvents normally have a very different polarity to that of the product, resulting in some general heuristics:
- if the feed is aqueous, the nonsolvent may be acetone or t-butanol - the feed has a solvent such as ethanol, the nonsolvent is usually water - If the feed is potentially ionic, the precipitation can be effected by excess salt
Furthermore:
- Precipitation increases as temperature decreases. - Precipitation of high molecular weight products is easier than of low molecular weight ones. - Precipitation tends to be easier if many solutes are present. - Precipitation from water is easier when the ionic strength is around 0.1 M.
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Crystallization
Crystallization tries to purify the product, not just to concentrate it, and is therefore one of the most important separation processes for specialty chemicals Crystallization aims at large crystals, that are easier to wash and filter (normally the next steps in the separation). Crystallization depends on three key factors:
- Solubility variation with temperature and solvent composition (an equilibrium factor parallel to the partition coefficient for extraction and the isotherm for adsorption). - Second, crystallization depends on the crystal growth rate. - Third, crystallization depends on the "cooling curve."
Solubility Variation
Usually, the solubility increases as temperature increases. By reducing the temperature or changing the solvent concentration, we can potentially initiate crystal formation. Solutions can often contain more solute than that present at saturation. Such supersaturated solutions are thermodynamically unstable, however, they can be metastable, a result of the surface energy of small crystals To overcome the thermodynamic barrier of metastability, larger seed crystals can be added to start the crystals growing in the supersaturated solution. Ideally, these seeds will be of pure product.
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initial temperature
seed mass
dimensionless time
final time
seed radius
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Penicillin Purification
How to isolate and purify the penicillin from the broth? Key to this purification is the recognition that penicillin is a carboxylic acid. When the pH is above about 5.5, the COOH group ionizes to COO- and the penicillin becomes water soluble. When the pH is below 5, the COOH group remains protonated, and the penicillin is more soluble in organic extraction solvents The first step is to separate the penicillin containing broth from the large biomass of micro-organisms. Because normal filters tend to plug, this separation involves adsorption of the microbes on diamataceous earth (FilterAid) and then filtration
The clarified broth is acidified and then extracted with amyl acetate. Because the acid form of the penicillin is less stable, this extraction should be as fast as possible. (The first amyl acetate extract is decolorized by adsorption on activated carbon) Then the amyl acetate is extracted with water at pH 7.5, so the product moves back into the water. This entire process is repeated until the penicillin is concentrated perhaps 100 times. The last aqueous extract may be dried as a crude product before it is redissolved Finally, butanol is added to the aqueous penicillin solution under a defined temperature profile to precipitate crystals of sodium or potassium penicillin
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