# Introduction to Chemical Engineering Processes/Unit Operation Reference

## What is a "Unit Operation"?

A unit operation is any part of potentially multiple-step process which can be considered to have a single function. Examples of unit operations include:

• Separation Processes
• Purification Processes
• Mixing Processes
• Reaction Processes
• Power Generation Processes
• Heat Exchangers

In general the ductwork between the processes is not explicitly included, though a single pipe can be analyzed for purposes of determining friction loss, heat losses, pressure drop, and so on.

Large processes are broken into unit operations in order to make them easier to analyze. The key thing to remember about them is that the conservation laws apply not only to the process as a whole but also to each individual unit operation.

The purpose of this section is not to show how to design these operations (that's a whole other course) but to give a general idea of how they work.

## Separation Processes

There are a large number of types of separation processes, including distillation, extraction, absorption, membrane filtration, and so on. Each of these can also be used for purification, to varying degrees.

### Separation by Flashing

A mixture of two liquids or a liquid and vapor can be separated by passing it to a flash drum at a fixed temperature and pressure. The mixture is allowed to reach equilibrium (or near it), and then the vapor exits the top and the liquid exits the bottom of the drum. This separates the components somewhat, provided that the temperature is chosen between the boiling temperatures of the components of the mixture at the pressure of the drum. The degree of separation depends on the composition of the mixture, the concentrations of the species in the mixture, and the temperature and pressure. Having data such as fugacity data or even vapor pressures for simple modelling like Raoult's Law is invaluable when choosing the operating conditions.

When a solution boils, the resulting gas is still a mixture, but the gaseous mixture will in general have more of the lower-boiling compound than the higher-boiling compound. Therefore, a higher-boiling compound can be separated from the lower-boiling compound by simply allowing part of the solution to boil and part to remain as liquid.

### Distillation

Distillation, like flashing, is a process which is generally used to separate a mixture of two or more liquids based on their boiling points. However, what happens in a distillation column is essentially a series of flashes, which are connected with recycle loops. The liquid from each tray comes to equilibrium (ideally) with the vapor, and the vapor rises up to the next tray and the liquid falls to the tray beneath it. Each tray has a different temperature because a reboiler on the bottom and a condenser at the top maintain a temperature gradient across the column (in certain separation setups one of these components is omitted).

Distillation is an unit operation, in which two constituent is separated by different boiling point.

The net result is, like flashing, more of the lower-boiling compound(s) will exit at the top of the column, and more of the higher-boiling compound(s) will fall to the bottoms. Since distillation is multiple flashes in a row, it is typically more effective than a single flash, although the latter may be sufficient depending on the purpose. Distillation columns are standard for many types of separations because it is relatively inexpensive for its efficacy. Distillation has a limit, however: non-ideal mixtures can form azeotropes. An azeotrope is a point at which when the solution boils, the vapor has the same composition as the liquid. Therefore no further separation can be done without another method or without using some special tricks.

Two examples of distillation processes are petroleum distillation and the production of alcoholic beverages. In the first case, oil is separated into its many components, with the lightest at the top and the heaviest on the bottom. In the latter, the gas is enriched in ethanol, which is later recondensed.

### Gravitational Separation

Gravitational separation takes advantage of the well-known effect of density differences: something that is less dense will float on something that is more dense. Therefore, if two immiscible liquids have significantly different densities, they can be separated by simply letting them settle, then draining the denser liquid out the bottom. Note that the key word here is immiscible; if the liquids are soluble in each other, then it is impossible to separate them by this method.

This method can also be used to separate out solids from a liquid mixture, but again the solids must not be soluble in the liquid (or must be less soluble than they are as present in the solution).

### Extraction

Extraction is the general practice of taking something dissolved in one liquid and forcing it to become dissolved in another liquid. This is done by taking advantage of the relative solubility of a compound between two liquids. For example, caffeine must be extracted from coffee beans or tea leaves in order to be used in beverages such as coffee or soda. The common method for doing this is to use supercritical carbon dioxide, which is able to dissolve caffeine as if it were a liquid. Then, in order to take the caffeine out, the temperature is lowered (lowering the "solubility" in carbon dioxide) and water is injected. The system is then allowed to reach equilibrium. Since caffeine is more soluble in water than it is in carbon dioxide, the majority of it goes into the water.

Extraction is also used for purification, if some solution is contaminated with a pollutant, the pollutant can be extracted with another, clean stream. Even if it is not very soluble, it will still extract some of the pollutant.

Another type of extraction is acid-base extraction, which is useful for moving a basic or acidic compound from a polar solvent (such as water) to a non-polar one. Often, the ionized form of the acid or base is soluble in a polar solvent, but the non-ionized form is not as soluble. The reverse is true for the non-ionized form. Therefore, in order to manipulate where the majority of the compound will end up, we alter the pH of the solution by adding acid or base.

For example, suppose you wanted to extract Fluoride (F-) from water into benzene. First, you would add acid, because when a strong acid is added to the solution it undergoes the following reaction with fluoride, which is practically irreversible:

${\displaystyle F^{-}+H_{3}O^{+}\rightarrow HF+H_{2}O}$

The hydrogen fluoride is more soluble in benzene than fluoride itself, so it would move into the benzene. The benzene and water fluoride solutions could then be separated by density since they're immiscible.

The term absorption is a generalization of extraction that can involve different phases (gas-liquid instead of liquid-liquid). However, the ideas are still the same.

### Membrane Filtration

A membrane is any barrier which allows one substance to pass through it more than another. There are two general types of membrane separators: those which separate based on the size of the molecules and those which separate based on diffusivity.

An example of the first type of membrane separator is your everyday vacuum cleaner. Vacuum cleaners work by taking in air laden with dust from your carpet. A filter inside the vacuum then traps the dust particles (which are relatively large) and allows the air to pass through it (since air particles are relatively small). A larger-scale operation that works on the same principle is called a fabric filter or "Baghouse", which is used in air pollution control or other applications where a solid must be removed from a gas.

Some fancy membranes exist which are able to separate hydrogen from a gaseous mixture by size. These membranes have very small pores which allow hydrogen (the smallest possible molecule, by molecular weight) to pass through by convection, but other molecules cannot pass through the pores and must resort to diffusion (which is comparatively slow). Hence a purified hydrogen mixture results on the other side.

Membranes can separate substances by their diffusivity as well, for example water may diffuse through a certain type of filter faster than ethanol, so if such a filter existed it could be used to enrich the original solution with ethanol.

## Purification Methods

In order to bring any product to market, it is necessary to purify it adequately. Without purification, people could get sick from eating foods, side-reactions could occur in industry which would cause safety concerns, or a scientist's research could be invalidated. Fortunately there are several methods used to purify things. The separation processes mentioned above are often used for this purpose, as are the following two processes:

Not to be confused with absorption, but adsorption is a process which separates components by their relative adhesiveness to a surface. An adsorption column is essentially a pipe filled with a certain material. When the contaminant flows by, it will bind to the material, and in this way the fluid flowing by is cleaned.

A major disadvantage to this method is that the material will always have a saturation point after which no more contaminant can latch on to it. At this point cleaning stops and therefore the spent material must be replaced by new material.

### Recrystallization

Recrystallization is the purification of substances by taking advantage of changes in solubility with respect to temperature.We take advantage of this by dissolving an impure compound and then lowering the temperature slowly. The solubility of most solid substances increases with temperature [1], so decreasing the temperature will cause the solubility of both the impurities and the substance to be purified to decrease. However, since there is likely much more of the impure substance present than impurities, the impure substance will crystallize out long before the impurities will. Therefore, as long as the temperature is not lowered too quickly, the impure substance will crystallize out in a purer form, while most impurities will remain in solution.

A disadvantage to this method is that it takes a long time to perform, but it is often the most effective method for obtaining a pure sample of a product.

## Reaction Processes

### Plug flow reactors (PFRs) and Packed Bed Reactors (PBRs)

A plug flow reactor is a (idealized) reactor in which the reacting fluid flows through a tube at a rapid pace, but without the formation of eddies characteristic of rapid flow. Plug flow reactors tend to be relatively easy to construct (they're essentially pipes) but are problematic in reactions which work better when reactants (or products!) are dilute.

Plug flow reactors can be combined with membrane separators in order to increase the yield of a reactor. The products are selectively pulled out of the reactor as they are made so that the equilibrium in the reactor itself continues to shift towards making more product.

A packed bed reactor is essentially a plug flow reactor packed with catalyst beads. They are used if, like the majority of reactions in industry, the reaction requires a catalyst to significantly progress at a reasonable temperature.

### Continuous Stirred-Tank Reactors (CSTRs) and Fluidized Bed Reactors (FBs)

A continuous stirred-tank reactor is an idealized reactor in which the reactants are dumped in one large tank, allowed to react, and then the products (and unused reactants) are released out of the bottom. In this way the reactants are kept relatively dilute, so the temperatures in the reactor are generally lower. This also can have advantages or disadvantages for the selectivity of the reaction, depending on whether the desired reaction is faster or slower than the undesired one.

CSTRs are generally more useful for liquid-phase reactions than PFRs since less transport power is required. However, gas-phase reactions are harder to control in a CSTR.

A fluidized bed reactor is, in essence, a CSTR which has been filled with catalyst. The same analogy holds between an FB and CSTR as does between a PFR and a PBR. Unlike CSTRs though, Fluidized beds are commonly used with gases; the gas is pumped in the bottom and bubbles through the catalyst on the way to the top outlet.

### Bioreactors

A bioreactor is a reactor that utilizes either a living organism or one or more enzymes from a living organism to accomplish a certain chemical transformation. Bioreactors can be either CSTRs (in which case they are known as chemostats) or PFRs.

Certain characteristics of a bioreactor must be more tightly controlled than they must be in a normal CSTR or PFR because cellular enzymes are very complex and have relatively narrow ranges of optimum activity. These include, but are not limited to:

1. Choice of organism. This is similar to the choice of catalyst for an inorganic reaction.
2. Strain of the organism. Unlike normal catalysts, organisms are very highly manipulable to produce more of what you're after and less of other products. However, also unlike normal catalysts, they generally require a lot of work to get any significant production at all.
3. Choice of substrate. Many organisms can utilize many different carbon sources, for example, but may only produce what you want from one of them.
4. Concentration of substrate and aeration. Two inhibitory effects exist which could prevent you from getting the product you're after. Too much substrate leads to the glucose effect in which an organism will ferment regardless of the air supply, while too much air will lead to the pasteur effect and a lack of fermentation.
5. pH and temperature: Bacterial enzymes tend to have a narrow range of optimal pH and temperatures, so these must be carefully controlled.

However, bioreactors have several distinct advantages. One of them is that enzymes tend to be stereospecific, so for example you don't get useless D-sorbose in the production of vitamin C, but you get L-sorbose, which is the active form. In addition, very high production capacities are possible after enough mutations have been induced. Finally, substances which have not been made artificially or which would be very difficult to make artificially (like most antibiotics) can be made relatively easily by a living organism.

## Heat Exchangers

In general, a heat exchanger is a device which is used to facilitate the exchange of heat between two mixtures, from the hotter one to the cooler one. Heat exchangers very often involve steam because steam is very good at carrying heat by convection, and it also has a high heat capacity so it won't change temperature as much as another working fluid would. In addition, though steam can be expensive to produce, it is likely to be less expensive than other working fluids since it comes from water.

### Tubular Heat Exchangers

A tubular heat exchanger is essentially a jacket around a pipe. The working fluid (often steam) enters the jacket on one side of the heat exchanger and leaves on the other side. Inside the pipe is the mixture which you want to heat or cool. Heat is exchanged through the walls of the device in accordance to the second law of thermodynamics, which requires that heat flow from higher to lower temperatures. Therefore, if it is desired to cool off the fluid in the pipe, the working fluid must be cooler than the fluid in the pipe.

Heat exchangers work because heat naturally flows from higher temperature to lower temperatures. Therefore if a hot fluid and a cold fluid are separated by a heat conducting surface heat can be transferred from the hot fluid to the cold fluid.

Tubular heat exchangers can be set up in two ways: co-current or counter-current. In a co-current setup, the working fluid and the fluid in the pipe enter on the same side of the heat exchanger. This setup is somewhat inefficient because as heat is exchanged, the temperature of the working fluid will approach that of the fluid in the pipe. The closer the two temperatures become, the less heat can be exchanged. Worse, if the temperatures become equal somewhere in the middle of the heat exchanger, the remaining length is wasted because the two fluids are at thermal equilibrium (no heat is released).

To help counteract these effects, one can use a counter-current setup, in which the working fluid enters the heat exchanger on one end and the fluid in the pipe enters at the other end. As an explanation for why this is more efficient, suppose that the working fluid is hotter than the fluid in the pipe, so that the fluid in the pipe is heated up. The fluid in the pipe will be at its highest temperature when it exits the heat exchanger, and at its coolest when it enters. The working fluid will follow the same trend because it cools off as it travels the length of the exchanger. Because it's counter-current, though, the fact that the working fluid cools off has less of an effect because it's exchanging heat with cooler, rather than warmer, fluids in the pipe.

 To do: Draw a diagram to help show how this works.