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Jump to: navigation, search Laboratory distillation set-up: 1: Heat source 2: Still pot 3: Still head 4: Thermometer/Boiling point temperature 5: Condenser 6: Cooling water in 7: Cooling water out 8: Distillate/receiving flask 9: Vacuum/gas inlet 10: Still receiver 11: Heat control 12: Stirrer speed control 13: Stirrer/heat plate 14: Heating (Oil/sand) bath 15: Stiring means e.g. magnetic follower (shown), anti-bumping granules or mechanical stirrer 16: Cooling bath. Distillation is a method of separating chemical substances based on differences in their volatilities in a boiling liquid mixture. Distillation usually forms part of a larger chemical process, and is thus referred to as a unit operation. Commercially, distillation has a number of uses. It is used to separate crude oil into more fractions for specific uses such as transport, power generation and heating. Water is distilled to remove impurities, such as salt from sea water. Air is distilled to separate its components - notably oxygen, nitrogen and argon - for industrial use. Distillation of fermented solutions has been used since ancient times to produce distilled beverages with a higher alcohol content.
Contents
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1 History 2 Applications of distillation 3 Idealized distillation model o 3.1 Batch distillation o 3.2 Continuous distillation o 3.3 General improvements 4 Laboratory scale distillation o 4.1 Simple distillation o 4.2 Fractional distillation o 4.3 Steam distillation o 4.4 Vacuum distillation o 4.5 Air-sensitive vacuum distillation
6 7 8 9
4.6 Short path distillation 4.7 Other types Azeotropic distillation o 5.1 Breaking an azeotrope with unidirectional pressure manipulation o 5.2 Pressure-swing Distillation Industrial distillation Distillation in food processing o 7.1 Distilled beverages References External links
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10 Gallery
[edit] History
The first pure distillation procedures for producing fully purified chemical substances were carried out by Muslim chemists for industrial purposes such as isolating natural esters (perfumes) and producing pure alcohol.[1] However, early forms of distillation were known to Babylonian alchemists in Mesopotamia (in what is now Iraq) from at least the 2nd millennium BC.[2] Distillation was later known to Greek alchemists from the 1st century AD,[3][4][5] and the later development of large-scale distillation apparatus occurred in response to demands for spirits.[3] Hypathia of Alexandria is credited with having invented an early distillation apparatus,[6] and the first exact description of apparatus for distillation is given by Zosimos of Alexandria in the fourth century.[5]
Distillation by retort using the alembic. In the 8th century, Muslim chemists were the first to invent pure distillation processes which were able to fully purify chemical substances.[1] The first among them was the Persian chemist Jabir ibn Hayyan (Geber) in Iran circa 800 AD, who is credited with the invention of numerous chemical apparatus and processes that are still in use today. In particular, his alembic was the first still with retorts which could fully purify chemicals, a precursor to the pot still, and its design has served as inspiration for modern micro-scale distillation apparatus such as the Hickman stillhead.[7] Petroleum was first distilled by another Muslim chemist al-Razi (Rhazes) in the 9th century, for producing kerosene,[8] while steam distillation was invented by Avicenna in the early 11th century, for producing essential oils.[9] As
alchemy evolved into the science of chemistry, vessels called retorts became used for distillations. Both alembics and retorts are forms of glassware with long necks pointing to the side at a downward angle which acted as air-cooled condensers to condense the distillate and let it drip downward for collection. Later, copper alembics were invented. Riveted joints were often kept tight by using various mixtures, for instance a dough made of rye flour.[10] These alembics often featured a cooling system around the beak, using cold water for instance, which made the condensation of alcohol more efficient. These were called pot stills. Today, the retorts and pot stills have been largely supplanted by more efficient distillation methods in most industrial processes. However, the pot still is still widely used for the elaboration of some fine alcohols such as cognac, Scotch whisky and some vodkas. Pot stills made of various materials (wood, clay, stainless steel) are also used by bootleggers in various countries. Small pot stills are also sold for the domestic production[11] of flower water or essential oils.
It is not possible to completely purify a mixture of components by distillation, as this would require each component in the mixture to have a zero partial pressure. If ultra-pure products are the goal, then further chemical separation must be applied.
least two output fractions, including at least one volatile distillate fraction, which has boiled and been separately captured as a vapor condensed to a liquid. There is always a bottoms (or residue) fraction, which is the least volatile residue that has not been separately captured as a condensed vapor.
Air condenser Vigreux column (usually laboratory scale only) Packed column (packed with glass beads, metal pieces, or other chemically inert material) Spinning band distillation system
As a result, simple distillation is usually used only to separate liquids whose boiling points differ greatly (rule of thumb is 25 C), [12] or to separate liquids from involatile solids or oils. For these cases, the vapor pressures of the components are usually sufficiently different that Raoult's law may be neglected due to the insignificant contribution of the less volatile component. In this case, the distillate may be sufficiently pure for its intended purpose.
Steam distillation of various aromatic herbs and flowers can result in two products; an essential oil as well as a watery herbal distillate. The essential oils are often used in perfumery and aromatherapy while the watery distillates have many applications in aromatherapy, food processing and skin care.
Dimethyl sulfoxide usually boils at 189 C. Under a vacuum, it distills off into the receiver at only 70 C. Perkin Triangle Distillation Setup 1: Stirrer bar/anti-bumping granules 2: Still pot 3: Fractionating column 4: Thermometer/Boiling point temperature 5: Teflon tap 1 6: Cold finger 7: Cooling water out 8: Cooling water in 9: Teflon tap 2 10: Vacuum/gas inlet 11: Teflon tap 3 12: Still receiver
This technique is also very useful for compounds which boil beyond their decomposition temperature at atmospheric pressure and which would therefore be decomposed by any attempt to boil them under atmospheric pressure.
Short path vacuum distillation apparatus with vertical condenser (cold finger), to minimize the distillation path; 1: Still pot with stirrer bar/anti-bumping granules 2: Cold finger - bent to direct condensate 3: Cooling water out 4: cooling water in 5: Vacuum/gas inlet 6: Distillate flask/Distillate. Short path distillation is a distillation technique that involves the distillate traveling a short distance, often only a few centimeters. A classic example would be a distillation involving the distillate traveling from one glass bulb to another, without the need for a condenser separating the two chambers. This technique is often used for compounds which are unstable at high temperatures. The Advantage is that the heating temperature can be considerably lower (at this reduced pressure) than the boiling point of the liquid at standard
pressure, and that the distillate only has to travel a short distance before condensing.
In rotary evaporation a vacuum distillation apparatus is used to remove bulk solvents from a sample. Typically the vacuum is generated by a water aspirator or a membrane pump. In a kugelrohr a short path distillation apparatus is typically used (generally in combination with a (high) vacuum) to distill high boiling (> 300 C) compounds. The apparatus consists of an oven in which the compound to be distilled is placed, a receiving portion which is outside of the oven, and a means of rotating the sample. The vacuum is normally generated by using a high vacuum pump. The process of reactive distillation involves using the reaction vessel as the still. In this process, the product is usually significantly lower-boiling than its reactants. As the product is formed from the reactants, it is vaporized and removed from the reaction mixture. This technique is an example of a continuous vs. a batch process; advantages include less downtime to charge the reaction vessel with starting material, and less workup. Destructive distillation involves the strong heating of solids (often organic material) in the absence of oxygen (to prevent combustion) to evaporate various high-boiling liquids, as well as thermolysis products. The gases evolved are cooled and condensed as in normal distillation. The destructive distillation of wood to give methanol is the root of its common name - wood alcohol. Pervaporation is a method for the separation of mixtures of liquids by partial vaporization through a non-porous membrane. Dry distillation, despite its name, is not truly distillation, but rather a chemical reaction known as pyrolysis in which solid substances are heated in a strongly reducing atmosphere and any volatile fractions are collected. Extractive distillation is defined as distillation in the presence of a miscible, high boiling, relatively non-volatile component, the solvent, that forms no azeotrope with the other components in the mixture. Flash evaporation (or partial evaporation) is the partial vaporization that occurs when a saturated liquid stream undergoes a reduction in pressure by passing through a throttling valve or other throttling device. This process is one of the simplest unit operations. Freeze distillation is an analogous method of purification using freezing instead of evaporation. It is not truly distillation, and
does not produce products equivalent to distillation. This process is used in the production of ice beer and ice wine to increase ethanol and sugar content, respectively. Codistillation is distillation which is performed on mixtures in which the two compounds are not miscible.
boiling point of the azeotrope is greater than the boiling point of either pure component. To break azeotropic distillations and cross distillation boundaries, such as in the DeRosier Problem, it is necessary to increase the composition of the light key in the distillate.
with
unidirectional
A vacuum distillation can be used to "break" an azeotropic mixture. Varying the temperature of the vapour generating flask when distilling an azeotrope from cold to the solutions boiling point does not produce a continuously sliding ratio of product to contaminate in the distillate. The two separate boiling points still remain, they merely overlap; these can be thought of as required activation energies for the release of a particular vapour. By exposing an azeotrope to a vacuum, it's possible to bias the boiling point of one away from the other by exploiting the difference between each components vapour pressure. When the bias is great enough, the two boiling points no longer overlap and so the azeotropic band disappears. This method is not without drawbacks. As an example, exposing a solution of water and ethanol to a 70 torr vacuum will allow for absolute ethanol to be distilled. However, due to the low pressure atmosphere, the ethanol vapour requires a significantly cooler condenser surface to liquefy, going from 78.3 C at atmospheric pressure to 24.5 C at 70 torr; failure to provide such results in the vapours passing through the condenser and into the vacuum source. This can also affect the efficiency of the condenser, as the liquefying temperature drops towards the minimum the condensing equipment can cool to, the thermal gradient across the liquefying surfaces reduces and, so with it, the rate at which heat can be extracted from the vapour. Conversely, increasing a distillation pressure can also break an azeotrope, but will bring with it the possibility of thermal decomposition, for organic compounds in particular, and may be more beneficial to high temperature tolerant distillations, such as those of the metallic salts.
manipulation of boiling points by altering the pressure of the atmosphere to which a solution is exposed. It might be chosen over pure vacuum distillation of an azeotrope if that solution, for instance, had such a low liquefying point at the pressure required to break the azeotrope that the equipment was unable to provide for it, allowing the product to stream out of the condenser and into the vacuum source. Here, rather than manipulate just one boiling point, one or more are altered, one after the other; with the number of pressure alternations being determined by the number of components in the feed solution considered to be contaminants. This could be beneficial to a purification as it is likely to create less extreme thermal requirements. Simply, instead of swinging distillation pressure in one direction alone in an attempt to break the azeotrope in one step, the break is performed in two or more steps with pressure swung in two directions to create an operating band centered around more accessible temperatures; perhaps going from a negative pressure to atmospheric and on to a positive pressure. In essence, pressure-swing distillation is an attempt to reduce extreme conditions by dispersing the manipulation load across the equipment generating the distillation environment. If a continuous feed is desired, or the distillation pressures required are extreme enough to warrant specialised design, each step may require a physically separate column. If only a batch run is required and the same column can perform under all the required pressures, this single column may suffice; with the vapour generating flask being emptied after the first distillation, the first distillate run back to the start and the distillation rerun under the second pressure conditions, and so on. Selection of which component the distillate should be biased towards may be made based on the energy required to evaporate it from the feed solution. Pressure-swing distillation is employed during the purification of ethyl acetate after its catalytic synthesis from ethanol.
Typical industrial distillation towers Main article: Continuous distillation Large scale industrial distillation applications include both batch and continuous fractional, vacuum, azeotropic, extractive, and steam distillation. The most widely used industrial applications of continuous, steady-state fractional distillation are in petroleum refineries, petrochemical and chemical plants and natural gas processing plants. Industrial distillation[15][16] is typically performed in large, vertical cylindrical columns known as distillation towers or distillation columns with diameters ranging from about 65 centimeters to 16 meters and heights ranging from about 6 meters to 90 meters or more. When the process feed has a diverse composition, as in distilling crude oil, liquid outlets at intervals up the column allow for the withdrawal of different fractions or products having different boiling points or boiling ranges. The "lightest" products (those with the lowest boiling point) exit from the top of the columns and the "heaviest" products (those with the highest boiling point) exit from the bottom of the column and are often called the bottoms. Diagram of a typical industrial distillation tower Large-scale industrial towers use reflux to achieve a more complete separation of products. Reflux refers to the portion of the condensed overhead liquid product from a distillation or fractionation tower that is
returned to the upper part of the tower as shown in the schematic diagram of a typical, large-scale industrial distillation tower. Inside the tower, the downflowing reflux liquid provides cooling and condensation of the upflowing vapors thereby increasing the efficacy of the distillation tower. The more reflux is provided for a given number of theoretical plates, the better is the tower's separation of lower boiling materials from higher boiling materials. Alternatively, the more reflux is provided for a given desired separation, the fewer theoretical plates are required. Such industrial fractionating towers are also used in air separation, producing liquid oxygen, liquid nitrogen, and high purity argon. Distillation of chlorosilanes also enables the production of high-purity silicon for use as a semiconductor. Section of an industrial distillation tower showing detail of trays with bubble caps Design and operation of a distillation tower depends on the feed and desired products. Given a simple, binary component feed, analytical methods such as the McCabe-Thiele method[16][17] or the Fenske equation[16] can be used. For a multi-component feed, simulation models are used both for design and operation. Moreover, the efficiencies of the vapor-liquid contact devices (referred to as "plates" or "trays") used in distillation towers are typically lower than that of a theoretical 100% efficient equilibrium stage. Hence, a distillation tower needs more trays than the number of theoretical vapor-liquid equilibrium stages. In industrial uses, sometimes a packing material is used in the column instead of trays, especially when low pressure drops across the column are required, as when operating under vacuum.
Large-scale, industrial vacuum distillation column[18] This packing material can either be random dumped packing (1-3" wide) such as Raschig rings or structured sheet metal. Liquids tend to wet the surface of the packing and the vapors pass across this wetted surface, where mass transfer takes place. Unlike conventional tray distillation in which every tray represents a separate point of vaporliquid equilibrium, the vapor-liquid equilibrium curve in a packed column is continuous. However, when modeling packed columns, it is useful to compute a number of "theoretical stages" to denote the separation efficiency of the packed column with respect to more traditional trays. Differently shaped packings have different surface areas and void space between packings. Both of these factors affect packing performance. Another factor in addition to the packing shape and surface area that affects the performance of random or structured packing is the liquid and vapor distribution entering the packed bed. The number of theoretical stages required to make a given separation is calculated using a specific vapor to liquid ratio. If the liquid and vapor are not evenly distributed across the superficial tower area as it enters the packed bed, the liquid to vapor ratio will not be correct in the packed bed and the required separation will not be achieved. The packing will appear to not be working properly. The height equivalent of a theoretical plate (HETP) will be greater than expected. The problem is not the packing itself but the mal-distribution of the fluids entering the packed bed. Liquid mal-distribution is more frequently the problem
than vapor. The design of the liquid distributors used to introduce the feed and reflux to a packed bed is critical to making the packing perform to it maximum efficiency. Methods of evaluating the effectiveness of a liquid distributor to evenly distribute the liquid entering a packed bed can be found in references.[19][20] Considerable work as been done on this topic by Fractionation Research, Inc. (commonly known as FRI).[21]
[edit] References
1. ^ a b Robert Briffault (1938). The Making of Humanity, p. 195. 2. ^ Martin Levey (1956). "Babylonian Chemistry: A Study of Arabic and
Second Millennium B.C. Perfumery", Osiris 12, p. 376-389. 3. ^ a b Colin Archibald Russell (2000). Chemistry, Society and Environment: A New History of the British Chemical Industry. Royal Society of Chemistry, p.69. ISBN 0854045996. 4. ^ Edgar Ashworth Underwood. Science, Medicine, and History: Essays on the Evolution of Scientific Thought and Medical. Oxford University Press, 251. 5. ^ a b Charles Simmonds (1919). Alcohol: With Chapters on Methyl Alcohol, Fusel Oil, and Spirituous Beverages. Macmillan and Co. Ltd, 6. 6. ^ Biology, Joan Solomon, Pat O'Brien, Peter Horsfall, Nelson Thornes, p.41 7. ^ Microscale Laboratory Techniques - Distillation from McMaster University 8. ^ Kasem Ajram (1992). Miracle of Islamic Science. Knowledge House Publishers, Appendix B. ISBN 0911119434. 9. ^ A. Wolf, G. A. Bray, B. M. Popkin (2007). "A short history of beverages and how our body treats them". Obesity Reviews. doi:10.1111/j.1467-789X.2007.00389.x. 10. ^ Sealing Technique, accessed 16 November 2006. 11. ^ Traditional Alembic Pot Still, accessed 16 November 2006.
13. ^ Fractional Distillation 14. ^ Spinning Band Distillation at B/R Instrument Corporation (accessed 8
September 2006)
ISBN 0-07-034909-6. 16. ^ a b c Perry, Robert H. and Green, Don W. (1984). Perry's Chemical Engineers' Handbook, 6th Edition, McGraw-Hill. ISBN 0-07-049479-7. 17. ^ Seader, J. D., and Henley, Ernest J.. Separation Process Principles. New York: Wiley. ISBN 0-471-58626-9. 18. ^ Energy Institute website page 19. ^ Random Packing, Vapor and Liquid Distribution: Liquid and gas distribution in commercial packed towers, Moore, F., Rukovena, F., Chemical Plants & Processing, Edition Europe, August 1987, p. 11-15 20. ^ Structured Packing, Liquid Distribution: A new method to assess liquid distributor quality, Spiegel, L., Chemical Engineering and Processing 45 (2006), p. 1011-1017 21. ^ Packed Tower Distributors: Commercial Scale Experiments That Provide Insight on Packed Tower Distributors, Kunesh, J. G., Lahm, L., Yanagi, T., Ind. Eng. Chem. Res., 1987, vol. 26, p. 1845-1850 FRI (click on "Available Materials" and scroll to "Staff Publications")
Alcohol distillation Introduction to Distillation, University of Newcastle upon Tyne, UK American Distilling Institute Essential and Fragrance Oils Distillation Extractive Distillation Pharmaceutical Alcohol Distillation Distillation - Food Applications Case Study: Petroleum Distillation Binary Vapor-Liquid Equilibrium Data (searchable database). Chemical Engineering Research Information Center. Retrieved on 5 May, 2007.
[edit] Gallery
Chemistry on its beginnings used retorts as laboratory equipment exclusively for distillation processes.
A rotary evaporator is able to distill solvents more quickly at lower temperatures through the use of a vacuum.
Distillation using semi-microscale apparatus. The jointless design eliminates the need to fit pieces together. The pear-shaped flask allows the last drop of residue to be removed, compared with a similarly-sized round-bottom flask The small holdup volume prevents losses. A pig is used to channel the various distillates into three receiving flasks. If necessary the distillation can be carried out under vacuum using the vacuum adapter at the pig. [show]
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Separation processes
Retrieved from "http://en.wikipedia.org/wiki/Distillation"Categories: Distillation | Separation processes | Unit operations | Chemical engineering | Alchemical processes | Laboratory techniques | Phase changes