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CHEMICAL AND PROCESS ENGINEERING

Ryszard Pohorecki Faculty of Chemical and Process Engineering, Warsaw University of Technology, Warsaw, Poland Martin Molzahn Formerly Engineering and Maintenance, BASF SE, Ludwigshafen, Germany Rafiqul Gani Department of Chemical and Biochemical Engineering, Technical University of Denmark, Lyngby, Denmark John Bridgwater Department of Chemical Engineering and Biotechnology, University of Cambridge, Cambridge, UK Keywords: Chemical engineering, process engineering, fluid flow, heat transfer, mass transfer, unit operations, transport phenomena, chemical reaction engineering, mathematical modeling, process development and optimization, environmental protection and process safety, chemical industry Contents 1. Definition and Scope 2. History 3. Fundamentals 3.1. Basic Concepts 3.2. Thermodynamics and Equilibrium 3.3. Heat and Mass Transfer 3.4. Balances 3.5. Fluid Flow 3.6. Chemical and Biochemical Kinetics and Catalysis 3.7. Mathematical modeling 4. Unit Operations 5. Chemical Reaction Engineering 6. Process Development and Optimization 7. Environmental Protection and Process Safety 8. Areas of application 9. Conclusion Related Chapters Glossary Bibliography Biographical Sketches

3.4. Balances Another important concept is that of balancing. A number of physical quantities (so

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called conservative quantities) may be balanced. A typical balance equation simply states, that the inflowing quantity must be equal to the sum of outflow, consumption or production and accumulation or loss (negative accumulation). In the case of mass, the mass conservation principle states that in chemical processes matter cannot be created or destroyed, therefore the mass balance is a simple one: the total mass entering the system must be equal to the mass leaving the system plus any mass retained (accumulated) within the system. Similarly one can make a balance of a constituent (taking into account the possibility of consumption or production of this constituent by a chemical reaction), energy (taking into account the possibility of converting one form of energy into another), momentum (the product of mass and its velocity), and other quantities (for more details see "Principles of momentum, mass and energy balances", "Generalized mass balances" and "Conservation equation for continuum"). For the description of dispersed phases one can use population balances. Population is a term describing any set of discrete (separate) elements like crystals, bubbles, drops, cells etc. A population may be divided into classes according to size, age, or another characteristic feature of its elements. The change in the number of elements belonging to different classes, due to inflow, outflow, accumulation, generation or consumption of the elements, may be determined using the population balance. Balances may be set up for the whole system (these are so called macroscopic, integral or shell balances) or for a very small (differential) part of the system (microscopic or differential balances, also known as equations of change). The differential balances allow for determination of the velocity, temperature and concentration profiles within the system. 3.5. Fluid Flow A very important part of science, describing the movement of fluids, is fluid mechanics. Almost any system, which takes part in an industrial (chemical of physical) process, consists of at least one fluid phase. Fluids are seldom immobile, they are easily set in motion either under the action of gravity (if different parts of fluid have different density; this is called natural convection), or under the action of pressure differences, caused by pumps or compressors (this is called forced convection). If the flow of a fluid is slow, it often is streamline (laminar), with one layer of fluid sliding smoothly along another; more often, however, a turbulent movement is observed, with bigger and smaller eddies moving around in a random way. The flow regime (laminar or turbulent) depends on the size of a duct or vessel, fluid density and viscosity, and fluid velocity. Fluid flow influences very strongly the rates of heat and mass transfer, described in Section 3.3. Movements of fluids enhance equalization of temperature and concentrations within a single phase, as well as heat and mass transfer between different phases. This is well known from the everydays life: we stir tea to speed up the dissolution of sugar. However, mechanical stirring cannot bring into contact separate molecules and this is a precondition of a chemical reaction. The process of mixing on the molecular scale, caused by diffusion enhanced by the small size, microscopic movements of fluid is called micromixing, as opposed to the large scale equalization of temperature and/or concentration, called macromixing.

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In industrial processes one often observes flow of mixtures of two or more phases gas bubbles in a liquid, emulsions formed by two immiscible liquids like oil and water, and so on. These multiphase flows are difficult to analyze and describe, and constitute an important challenge for the fluid mechanics. Another important field is that of interaction of a fluid with particles of a solid phase or elements of another fluid phase, suspended in the first one. This again is a difficult problem, especially in the case of dense suspensions. These interactions may involve mass transfer (e.g. dissolution of solid particles or crystal growth), deformation and breakage of bubbles or drops and so on. For more information see "Fluid mechanics", "Hydrodynamics", "Multiphase flow", "Liquid-liquid flows" and "Influence of mixing phenomena on chemical reactions". 3.6. Chemical and Biochemical Kinetics and Catalysis Any chemical or biochemical reaction proceeds at a certain rate. This rate is generally dependent on temperature and concentrations of reacting species, called reactants. Reactants consumed in the reaction are its substrates; those produced by the reaction are called products. There may be desired products, which we wish to obtain, and undesired by-products, which have to be separated from the desired products after the reaction is completed. The measurements, analysis and description of the reaction rates are the tasks of chemical (or biological) kinetics. In order to properly design a chemical reactor or bioreactor, the rate must be known and described by a suitable rate equation. The quantities of reactants consumed or produced in a reaction are related by a stoichiometric equation. Sometimes reactions proceed in a single step, these are called elementary reaction. A reaction involving several elementary steps is called non-elementary. If a non-elementary reaction involves very many repeated steps it is called chain reaction. Bioreactions are normally complicated non-elementary reactions. Biochemical kinetics describes not only the rates of bioreactions, but also the rate of growth of cell populations, e.g. the rate of growth or microbial cultures. This is very important for the design of bioreactors used for production of biomass, like, for example, barm yeast. Many reactions are accelerated (or, sometimes, hindered), by the presence of some substances, called catalysts. A catalyst is neither substrate nor product of the reaction, thus apparently does not take past in it. However, it does take part in some of the reaction steps (being consumed in one step and restored in another), and thus alters the overall reaction rate. Catalytic substances need not be present in large amounts, and, as mentioned above, are not consumed in the overall reaction (although may get deactivated after some time.). They are often introduced to the reacting system on the surface of so called carriers solid elements like grains, rings, platelets, etc., made of, for example, ceramics, usually porous to increase the catalyzing surface. In such cases the reacting substances have to be brought into contact with the catalytic surface, and products have to be removed from there, therefore the overall observed reaction rate shall be influenced by the rate of mass transfer processes (see Section 3.3). Also heat transfer rate may influence the observable reaction rate.

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Mass (and heat) transfer rate may also influence the overall rate in the case of reactions, whose substrates are introduced to the system in separate phases for example one substrate is gaseous, and another is liquid. The analysis of the reaction rate in such cases is the subject of so called macrokinetics. For more information see "Chemical and biochemical kinetics and macrokinetics" and "Catalysis and biocatalysis". 3.7. Mathematical modeling Balances, equilibrium relationships and expressions describing the rate of processes (e.g. the rate of chemical reactions, or the rate of mass and/or energy transfer) are normally described in terms of mathematical equations. A set of such equations, describing a given process, is called a mathematical model of the process. By solving the equations constituting the mathematical model on can get information about the behavior of the system, its performance in the given process, its reaction to external influence etc. This way a chemical engineer can design and control industrial processes. A useful tool in mathematical modeling is the similarity theory. This theory states that the mathematical description of a process may often be simplified if the process is described in terms of certain groups of parameters rather than in terms of these parameters separately. As an example, the so called Reynolds number characterizing fluid flow, is the product of characteristic geometrical dimension, density and velocity of the fluid, divided by the fluid viscosity. Such groups of parameters, usually named after outstanding scientists, are called similarity criteria. According to the similarity theory, if a process takes place in two different systems, it will proceed in a similar way provided the similarity criteria for both systems are equal. This is very important, since in theory it allows to foresee the behavior of a bigger system (e.g. an industrial apparatus) on the basis of laboratory experiments in a smaller system (this is called scaling up of a process). This principle has been successfully exploited in the design of ships and aircraft (investigation of small models of planes in so called wind tunnels helps to design big planes). Unfortunately, chemical plants cannot usually be scaled up in this way, since it is impossible to ensure equal values of all the similarity criteria involved in both systems. Nevertheless, similarity criteria are often employed to describe at least partly the behavior of the industrial systems. The development of powerful computers considerably increased the possibilities of mathematical modeling of industrial processes. For example, in the field of fluid mechanics it made possible to analyze and visualize the flows of fluids in industrial equipment (so called CFD, Computational Fluid Dynamics). Similarly, the achievements of computational chemistry made possible the design of specially "tailored" molecules (e.g. potential drugs, catalysts, etc.). Nowadays chemical engineers develop the idea of multiscale modeling, i.e. mathematical modeling of processes from the molecular to the industrial scale. As mentioned before, this may become the "third paradigm" of chemical engineering. For more information see "Chemical engineering in 2010 quo vamus", "Multi-scale modeling", and "Molecular simulations".

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4. Unit Operations The concept of unit operations has already been introduced in Point 2. This concept consists in splitting of a complex industrial process into individual elementary steps, called unit operations. These unit operations can then be studied separately, their principles being largely independent of the kind of the material processed. Moreover, one finds the same unit operations in many widely different industrial processes. The concept of unit operation significantly simplifies the study of a relatively small number of elementary steps, of which the complex processes consist. The unit operations may be classified in two ways: according to the underlying physical or physicochemical principles, or according to the phases being operated upon. To better explain the concept of unit operations, the most common operations shall be briefly described below. Mechanical operations The most common operations are those related to the handling of fluids: transport of fluids (gases or liquids) through pipelines, storage of fluids, pumping of liquids and compressing of gases. The underlying physical principles are those of fluid mechanics and thermodynamics. Another very common group is that related to the handling of solids, especially granular or powdered solid materials. Here belong transport and storage of solids, size reduction (by crushing, grinding and milling) and size enlargement, mixing of solids and fluidization. Fluidization is a very important operation, frequently used in some branches of industry. It consists in suspending granular or powdered solid in an up-flowing stream of fluid; the suspension called a fluidized phase (or fluidized bed) ensures particularly suitable conditions to carry out chemical reactions between solid and fluid phases. Another important group is related to the separation of solids from liquids by filtration, centrifugation, sedimentation (separation of solid as a sediment under the action of gravity), classification (separation by sedimentation with simultaneous segregation of solid particles according to the grain size), and flotation. The latter operation exploits differences in wettability of solids by liquids to separate different solid materials from one another. A gas (usually air) is bubbled through a layer of liquid (usually water), in which solid particles are suspended. Particles easily wetted by the liquid (called hydrophilic) remain in the suspension, whereas those poorly wetted (called hydrophobic) stick to the air bubbles, and are carried upwards by them. The poorly wetted particles can by removed from the top of the flotation apparatus in a layer of foam formed by the bubbles. This operation is often used for the enrichment of the metal ores. For more information see "Handling of fluids", "Handling of solids and transport", "Microfiltration". Heat transfer operations form another very common group of operations. Here belong heating and cooling evaporation, vapor condensation and refrigeration. As these terms are commonly known, they need no explanation. The underlying scientific principles are those of heat transfer and thermodynamics. Some operations, such as cooling of hot water by partial evaporation, involve also mass transfer. This way of cooling water is commonly employed in industry to re-cool water used previously to remove heat from hot process streams or heat generating processes, so

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that water may circulate in a closed loop, which is essential for water economy and environment protection. More information can be found in "Heat transfer" and "Evaporation and condensation and Refrigeration". Mass transfer operations The largest group of unit operations is that of operations based on mass transfer. They are most often used for separation of constituents of complex mixtures, and for purification of the separated components. One of the oldest unit operations is distillation. It consists in partial evaporation of a liquid mixture, and condensation of the produced vapor. As mentioned in Section 3.2, a vapor above a liquid phase has normally other composition than the liquid it is richer in more volatile component. Thus the condensed vapor (called distillate) differs in composition from the original liquid (called feed) and from the remaining part of liquid (called residue, bottom product, or waste). Distillation has been used for centuries to produce alcoholic liquors, it is also widely used in petroleum industry. Distillation is an energy consuming process, as evaporation requires a supply of heat, which can only partly be recuperated during condensation. Also the concentration difference achieved is limited. An improved version of distillation is called rectification, which in fact is a kind of multiple distillation process. Rectification is usually carried out in vertical columns, divided into several compartments by horizontal partition plates (called trays). On each tray the vapor generated on the tray immediately below meets the liquid flowing from the tray immediately above and, while partially condensing, causes partial evaporation of the liquid. Thus the liquid phase (called reflux) flows downwards from the top of the column, while the vapor phase flows upwards from the bottom, where it is generated in a reboiler. Such flow of two phases in opposite directions is called counter current flow (as opposite to co-current flow, where two phases flow alongside in same direction). On each tray a state close to thermodynamic equilibrium attained; the extent of equilibration is called plate efficiency. This way of conducting an operation by contacting phases in a sequence of successive steps or stages is called stepwise operation. (See also "Separation processes", "Distillation and rectification", "Batch distillation", "Continuous distillation processes"). In a similar, stepwise way, another operation, called liquid extraction, may be carried out. In this operation two streams of immiscible liquids (e.g. water and organic liquid such as benzene) are contacted to remove a component of a liquid mixture by a solvent, in which it is more soluble. The operation may be conducted either counter currently or co-currently, the solvent rich in the extracted component is called extract, while the original mixture, stripped of this component, is called raffinate. (See "Mass transfer operations: absorption and extraction", "Liquid-liquid extraction"). The operation of extracting a component from a solid by dissolving it in a liquid is called leaching. This operation is applied on an enormous scale to extract copper from the copper ore this field of application is called hydrometallurgy.

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A component of a gaseous mixture can be removed from the gas in operations called absorption and adsorption. The former consists in dissolving the component in question in a liquid solvent (called absorbent), in which it is more soluble than other components of the original mixture; the latter consists in binding a component on the surface of a solid (called adsorbent). In both cases the removed component may be recuperated in an operation called desorption. Absorption is used on a large scale to purify industrial synthesis gases in, e.g., ammonia industry, or to separate carbon dioxide from flue gases (carbon dioxide is a greenhouse gas). (See "Mass transfer operations: absorption and extraction", "Absorption equipment").

Figure 2. A carbon dioxide absorption/desorption plant (photo A. Furdal, courtesy of the Pulawy Nitrogen Works, Pulawy, Poland). Despite the similarity of names, the equipment used to carry out absorption and adsorption is, of course, quite different, and so is the mechanism of binding the separated component by the liquid absorbent and solid adsorbent. Both operations, however, are based on mass transfer (or mass exchange) between different phases. Many solid products, such as common salt, sugar, a number of pharmaceuticals, are produced by crystallization from a solution. In order to produce crystals of desired size and shape, a thorough knowledge of the principles of mass transfer and fluid mechanics is necessary. See also "Heat and mass transfer operations crystallization". The crystals produced are, or course, wet, and have to be dried. The operation of drying is common not only in chemical industry, but also in the production of food, pharmaceuticals, etc. Such common product as soluble coffee is produced by a special kind of drying operation, called spray drying. In recent years, a number of operations known under a common name of membrane separations have been quickly developing. They consist in using a diaphragm, called membrane, for separation of gaseous or liquid mixtures. A membrane, made of polymer, ceramics, or even metal, has to be semi-permeable, i.e. it has to allow passage of some components of the mixture, while retaining other components. Membrane separations are used on a very large scale for water desalination, i.e. production of drinking water from sea water. See also "Mass transfer operations membrane separations". Another quickly developing group of operations are so called hybrid separation processes. They consist in combining two different processes in one operation for example distillation with membrane separation, or distillation with chemical reaction (so called reactive distillation). See also "Multifunctional reactors". This short overview is by no means exhaustive there is a number of less common

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operations, and new operations are constantly developing. It is hoped, however that this description shall give the reader an idea of the most important unit operations. 1. Definition and Scope
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5. Chemical Reaction Engineering

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