Reflux

Last updated December 02, 2022

Reflux is a technique involving the condensation of vapors and the return of this condensate to the system from which it originated. It is used in industrial^[1] and laboratory^[2] distillations. It is also used in chemistry to supply energy to reactions over a long period of time.

Reflux in industrial distillation

The term reflux^[1]^[3]^[4] is very widely used in industries that utilize large-scale distillation columns and fractionators such as petroleum refineries, petrochemical and chemical plants, and natural gas processing plants.

In that context, reflux refers to the portion of the overhead liquid product from a distillation column or fractionator that is returned to the upper part of the column as shown in the schematic diagram of a typical industrial distillation column. Inside the column, the downflowing reflux liquid provides cooling and condensation of the upflowing vapors thereby increasing the efficiency of the distillation column.

The more reflux provided for a given number of theoretical plates, the better is the column's separation of lower boiling materials from higher boiling materials. Conversely, for a given desired separation, the more reflux is provided, the fewer theoretical plates are required.^[5]

Reflux in chemical reactions

Laboratory reflux apparatus. Ruckflusskuhler.jpg — Laboratory reflux apparatus.

A mixture of reactants and solvent is placed in a suitable vessel, such as a round bottom flask. This vessel is connected to a water-cooled condenser, which is typically open to the atmosphere at the top. The reaction vessel is heated in order to boil the reaction mixture; vapours produced from the mixture are condensed by the condenser, and return to the vessel through gravity. The purpose is to thermally accelerate the reaction by conducting it at an elevated, controlled temperature (i.e. the solvent's boiling point) and ambient pressure without losing large quantities of the mixture.^[6]

The diagram shows a typical reflux apparatus. It includes a water bath to indirectly heat the mixture. As many solvents used are flammable, direct heating with a Bunsen burner is not generally suitable, and alternatives such as a water bath, oil bath, sand bath, electric hot plate or heating mantle are employed.^[6]

Reflux in laboratory distillation

The apparatus shown in the diagram represents a batch distillation as opposed to a continuous distillation. The liquid feed mixture to be distilled is placed into the round-bottomed flask along with a few anti-bumping granules, and the fractionating column is fitted into the top. As the mixture is heated and boils, vapor rises up the column. The vapor condenses on the glass platforms (known as plates or trays) inside the column and runs back down into the liquid below, thereby refluxing the upflowing distillate vapor. The hottest tray is at the bottom of the column and the coolest tray is at the top. At steady state conditions, the vapor and liquid on each tray is at equilibrium. Only the most volatile of the vapors stays in gaseous form all the way to the top. The vapor at the top of the column then passes into the condenser, where it cools until it condenses into a liquid. The separation can be enhanced with the addition of more trays (to a practical limitation of heat, flow, etc.). The process continues until all the most volatile components in the liquid feed boil out of the mixture. This point can be recognized by the rise in temperature shown on the thermometer. For continuous distillation, the feed mixture enters in the middle of the column.

Reflux in beverage distillation

By controlling the temperature of the condenser, often called a dephlegmator, a reflux still may be used to ensure that higher boiling point components are returned to the flask while lighter elements are passed out to a secondary condenser. This is useful in producing high quality alcoholic beverages, while ensuring that less desirable components (such as fusel alcohols) are returned to the primary flask. For high quality neutral spirits (such as vodka), or post distillation flavored spirits (gin, absinthe), a process of multiple distillations or charcoal filtering may be applied to obtain a product lacking in any suggestion of its original source material for fermentation. The geometry of the still also plays a role in determining how much reflux occurs. In a pot still , if the tube leading from the boiler to the condenser, the lyne arm, is angled upward, more liquid will have a chance to condense and flow back into the boiler leading to increased reflux. Typical results can increase production as high as 50% over the basic worm type condenser. The addition of a copper "boiling ball" in the path creates an area where expansion of gasses into the ball causes cooling and subsequent condensation and reflux. In a column still, the addition of inert materials in the column (e.g., packing) creates surfaces for early condensation and leads to increased reflux.^{[ citation needed ]}

Gallery

Toluene is refluxed with sodium-benzophenone desiccant before it is distilled to give pure oxygen- and water-free toluene.
Industrial fractionating columns all of which use reflux
Organic synthesis apparatus using reflux

Related Research Articles

Distillation, or classical distillation, is the process of separating the components or substances from a liquid mixture by using selective boiling and condensation. Dry distillation is the heating of solid materials to produce gaseous products. Dry distillation may involve chemical changes such as destructive distillation or cracking and is not discussed under this article. Distillation may result in essentially complete separation, or it may be a partial separation that increases the concentration of selected components in the mixture. In either case, the process exploits differences in the relative volatility of the mixture's components. In industrial applications, distillation is a unit operation of practically universal importance, but it is a physical separation process, not a chemical reaction.

Fractional distillation is the separation of a mixture into its component parts, or fractions. Chemical compounds are separated by heating them to a temperature at which one or more fractions of the mixture will vaporize. It uses distillation to fractionate. Generally the component parts have boiling points that differ by less than 25 °C (45 °F) from each other under a pressure of one atmosphere. If the difference in boiling points is greater than 25 °C, a simple distillation is typically used. It is used to refine crude oil.

A fractionating column or fractional column is an essential item used in the distillation of liquid mixtures to separate the mixture into its component parts, or fractions, based on the differences in volatilities. Fractionating columns are used in small scale laboratory distillations as well as large scale industrial distillations.

A still is an apparatus used to distill liquid mixtures by heating to selectively boil and then cooling to condense the vapor. A still uses the same concepts as a basic distillation apparatus, but on a much larger scale. Stills have been used to produce perfume and medicine, water for injection (WFI) for pharmaceutical use, generally to separate and purify different chemicals, and to produce distilled beverages containing ethanol.

The Liebig condenser or straight condenser is a piece of laboratory equipment, specifically a condenser consisting of a straight glass tube surrounded by a water jacket.

Vacuum distillation is distillation performed under reduced pressure, which allows the purification of compounds not readily distilled at ambient pressures or simply to save time or energy. This technique separates compounds based on differences in their boiling points. This technique is used when the boiling point of the desired compound is difficult to achieve or will cause the compound to decompose. Reduced pressures decrease the boiling point of compounds. The reduction in boiling point can be calculated using a temperature-pressure nomograph using the Clausius–Clapeyron relation.

<span class="mw-page-title-main">Rotary evaporator</span>

A rotary evaporator (rotovap) is a device used in chemical laboratories for the efficient and gentle removal of solvents from samples by evaporation. When referenced in the chemistry research literature, description of the use of this technique and equipment may include the phrase "rotary evaporator", though use is often rather signaled by other language.

Steam distillation is a separation process that consists in distilling water together with other volatile and non-volatile components. The steam from the boiling water carries the vapor of the volatiles to a condenser; both are cooled and return to the liquid or solid state, while the non-volatile residues remain behind in the boiling container.

Continuous distillation, a form of distillation, is an ongoing separation in which a mixture is continuously fed into the process and separated fractions are removed continuously as output streams. Distillation is the separation or partial separation of a liquid feed mixture into components or fractions by selective boiling and condensation. The process produces at least two output fractions. These fractions include at least one volatile distillate fraction, which has boiled and been separately captured as a vapor condensed to a liquid, and practically always a bottoms fraction, which is the least volatile residue that has not been separately captured as a condensed vapor.

The Dean–Stark apparatus, Dean–Stark receiver, distilling trap, or Dean–Stark Head is a piece of laboratory glassware used in synthetic chemistry to collect water from a reactor. It is used in combination with a reflux condenser and a distillation flask for the separation of water from liquids. This may be a continuous removal of the water that is produced during a chemical reaction performed at reflux temperature, such as in esterification reactions. It was invented by the American chemists Ernest Woodward Dean (1888–1959) and David Dewey Stark (1893–1979) in 1920 for determination of the water content in petroleum.

In pre-modern chemistry and alchemy, cohobation was the process of repeated distillation of the same matter, with the liquid drawn from it; that liquid being poured again and again upon the matter left at the bottom of the vessel. Cohobation is a kind of circulation, only differing from it in this, that the liquid is drawn off in cohobation, as in common distillation, and thrown back again; whereas in circulation, it rises and falls in the same vessel, without ever being drawn out.

<span class="mw-page-title-main">Round-bottom flask</span>

Round-bottom flasks are types of flasks having spherical bottoms used as laboratory glassware, mostly for chemical or biochemical work. They are typically made of glass for chemical inertness; and in modern days, they are usually made of heat-resistant borosilicate glass. There is at least one tubular section known as the neck with an opening at the tip. Two- or three-necked flasks are common as well. Round bottom flasks come in many sizes, from 5 mL to 20 L, with the sizes usually inscribed on the glass. In pilot plants even larger flasks are encountered.

Batch distillation refers to the use of distillation in batches, meaning that a mixture is distilled to separate it into its component fractions before the distillation still is again charged with more mixture and the process is repeated. This is in contrast with continuous distillation where the feedstock is added and the distillate drawn off without interruption. Batch distillation has always been an important part of the production of seasonal, or low capacity and high-purity chemicals. It is a very frequent separation process in the pharmaceutical industry.

The McCabe–Thiele method is a chemical engineering technique for the analysis of binary distillation. It uses the fact that the composition at each theoretical tray is completely determined by the mole fraction of one of the two components and is based on the assumption of constant molar overflow, which requires that:

Spinning band distillation is a technique used to separate liquid mixtures which are similar in boiling points. When liquids with similar boiling points are distilled, the vapors are mixtures, and not pure compounds. Fractionating columns help separate the mixture by allowing the mixed vapors to cool, condense, and vaporize again in accordance with Raoult's law. With each condensation-vaporization cycles, the vapors are enriched in a certain component. A larger surface area allows more cycles, improving separation.

A theoretical plate in many separation processes is a hypothetical zone or stage in which two phases, such as the liquid and vapor phases of a substance, establish an equilibrium with each other. Such equilibrium stages may also be referred to as an equilibrium stage, ideal stage, or a theoretical tray. The performance of many separation processes depends on having series of equilibrium stages and is enhanced by providing more such stages. In other words, having more theoretical plates increases the efficiency of the separation process be it either a distillation, absorption, chromatographic, adsorption or similar process.

An evaporator is a device used to turn the liquid form of a chemical substance, such as water, into a vapor.

In chemistry, a condenser is laboratory apparatus used to condense vapors – that is, turn them into liquids – by cooling them down.

In systems involving heat transfer, a condenser is a heat exchanger used to condense a gaseous substance into a liquid state through cooling. In so doing, the latent heat is released by the substance and transferred to the surrounding environment. Condensers are used for efficient heat rejection in many industrial systems. Condensers can be made according to numerous designs, and come in many sizes ranging from rather small (hand-held) to very large. For example, a refrigerator uses a condenser to get rid of heat extracted from the interior of the unit to the outside air.

Refining of crude oils essentially consists of primary separation processes and secondary conversion processes. The petroleum refining process is the separation of the different hydrocarbons present in the crude oil into useful fractions and the conversion of some of the hydrocarbons into products having higher quality performance. Atmospheric and vacuum distillation of crude oils are the main primary separation processes producing various straight runproducts, e.g., gasoline to lube oils/vacuum gas oils. Distillation of crude oil is typically performed first under atmospheric pressure and then under a vacuum. Low boiling fractions usually vaporize below 400°C at atmospheric pressure without cracking the hydrocarbon compounds. Therefore, all the low boiling fractions of crude oil are separated by atmospheric distillation. A crude distillation unit (CDU) consists of pre-flash distillation column. The petroleum products obtained from the distillation process are light, medium, and heavy naphtha, kerosene, diesel, and oil residue.

References

1 2 Kister, Henry Z. (1992). Distillation Design (1st ed.). McGraw-Hill. ISBN 0-07-034909-6.
↑ Krell, Erich. (1982). Handbook of laboratory distillation : with an introduction into the pilot plant distillation ([3rd] completely rev. 2nd ed.). Amsterdam: Elsevier Scientific Pub. Co. ISBN 978-0-08-087549-1. OCLC 305628802.
↑ Perry, Robert H. & Green, Don W. (1984). Perry's Chemical Engineers' Handbook (6th ed.). McGraw-Hill. ISBN 0-07-049479-7.
↑ King, C. Judson (Cary Judson), 1934- (1980). Separation processes (2d ed.). New York: McGraw-Hill. ISBN 0-07-034612-7. OCLC 4882985.{{cite book}}: CS1 maint: multiple names: authors list (link)
↑ Towler, Gavin P. (2008). Chemical engineering design : principles, practice and economics of plant and process design. Sinnott, R. K. Amsterdam: Elsevier/Butterworth-Heinemann. ISBN 978-0-08-055695-6. OCLC 191735762.
1 2 "What is Reflux?". University of Toronto Scarborough - Chemistry Online. Retrieved October 21, 2017.

v t e Distillation
Principles	Raoult's law Dalton's law Reflux Fenske equation McCabe–Thiele method Theoretical plate Partial pressure Vapor–liquid equilibrium
Industrial processes	Batch distillation Continuous distillation Fractionating column Spinning cone
Laboratory methods	Alembic Kugelrohr Rotary evaporator Spinning band distillation Still
Techniques	Azeotropic Catalytic Destructive Dry Extractive Fractional Reactive Salt-effect Steam-based Vacuum-based