Chemical material balance

Some authors [29, 33] considered this process as stoichiometric which, under conditions of in situ combustion, could be described by the chemical material balance equation. Taking into account that in burning of petroleum residues (coke-CH)n, the compounds CO2, CO and H2O form, the authors obtained the following equation to describe the process of combustion of coke residue in situ ... 

The differential material balances contain a large number of physical parameters describing the structure of the porous medium, the physical properties of the gaseous mixture diffusing through it, the kinetics of the chemical reaction and the composition and pressure of the reactant mixture outside the pellet. In such circumstances it Is always valuable to assemble the physical parameters into a smaller number of Independent dimensionless groups, and this Is best done by writing the balance equations themselves in dimensionless form. The relevant equations are (11.20), (11.21), (11.22), (11.23), (11.16) and the expression (11.27) for the effectiveness factor. 

A typical material balance as well as chemical compositions are given in Table 5. The raw materials are metered into the makeup tanks in the proper ratios. Crysta11i2ation takes place in a separate crysta11i2er. An intermediate aging step at ambient temperature may be requited for the synthesis of certain high purity 2eobtes. 

If the T and P of a multiphase system are constant, then the quantities capable of change are the iadividual mole numbers of the various chemical species / ia the various phases p. In the absence of chemical reactions, which is assumed here, the may change only by iaterphase mass transfer, and not (because the system is closed) by the transfer of matter across the boundaries of the system. Hence, for phase equUibrium ia a TT-phase system, equation 212 is subject to a set of material balance constraints ... 

Equation 235 is the basic expression of material balance for a closed system in which r chemical reactions occur. It asserts that ia such a system... 

The general criterion of chemical reaction equiUbria is the same as that for phase equiUbria, namely that the total Gibbs energy of a closed system be a minimum at constant, uniform T and P (eq. 212). If the T and P of a siagle-phase, chemically reactive system are constant, then the quantities capable of change are the mole numbers, n. The iadependentiy variable quantities are just the r reaction coordinates, and thus the equiUbrium state is characterized by the rnecessary derivative conditions (and subject to the material balance constraints of equation 235) where j = 1,11,.. ., r ... 

The use of the computer in the design of chemical processes requires a framework for depiction and computation completely different from that of traditional CAD/CAM appHcations. Eor this reason, most practitioners use computer-aided process design to designate those approaches that are used to model the performance of individual unit operations, to compute heat and material balances, and to perform thermodynamic and transport analyses. Typical process simulators have, at their core, techniques for the management of massive arrays of data, computational engines to solve sparse matrices, and unit-operation-specific computational subroutines. 

Raw material costs should be estimated by direct computation from flow rates and material prices. The flow rates are deterrnined from flow sheet material balances. The unit prices are obtained from vendors, company purchasing departments, or the Chemical Marketing Reporter. For captive raw materials produced internally, a suitable transfer price must be estabHshed. Initial catalyst charges can be treated as a start-up expense, working capital component, or depreciable capital, depending on the expected catalyst life and cost. Makeup catalyst is frequendy treated as a raw material. 

Since the system is closed and without chemical reaction, material balances require that... 

Formulate the constraining material-balance equations, based on conservation of the total number of atoms of each element in a system comprised of w elements. Let subscript k identify a particular atom, and define Ai as the total number of atomic masses of the /cth element in the feed. Further, let a be the number of atoms of the /cth element present in each molecule of chemical species i. The material balance for element k is then... 

If species i is an element, AG/ is zero. There are N equilibrium equations (Eqs. [4-355]), one for each chemical species, and there are w material-balance equations (Eqs. [4-353]), one for each element—a total of N + to equations. The unknowns in these equations are the (note that y, = of which there are N, and the Xi, of which... 

The yield in a chemical reaction determines the quantities of materials in the material balance. Assumed yields are used to obtain approximate exploratoiy estimates. In this case, possible ranges should be given. Firmer estimates require yields based on laboratoiy or, preferably, pilot-plant work. 

For each stage J, the following 2C -1- 3 component material-balance (M), phase-equilibrium (E), mole-fraction-summation (S), and energy-balance (H) equations apply, where C is the number of chemical species ... 

For fast irreversible chemical reactions, therefore, the principles of rigorous absorber design can be applied by first estabhshing the effects of the chemical reaction on /cl and then employing the appropriate material-balance and rate equations in Eq. (14-71) to perform the integration to compute the required height of packing. 

To isolate a system for study, the system is separated from the surroundings by a boundary or envelope that may either be real (e.g., a reactor vessel) or imaginary. Mass crossing the boundaiy and entering the system is part of the mass-in term. The equation may be used for any compound whose quantity does not change by chemical reaction or for any chemical element, regardless of whether it has participated in a chemical reaction. Furthermore, it may be written for one piece of equipment, several pieces of equipment, or around an entire process (i.e., a total material balance). 

An example adapted from Verneuil, et al. (Verneuil, V.S., P. Yan, and F. Madron, Banish Bad Plant Data, Chemical Engineeiing Progress, October 1992, 45-51) shows the impact of flow measurement error on misinterpretation of the unit operation. The success in interpreting and ultimately improving unit performance depends upon the uncertainty in the measurements. In Fig. 30-14, the materi balance constraint would indicate that S3 = —7, which is unrealistic. However, accounting for the uncertainties in both Si and S9 shows that the value for S3 is —7 28. Without considering uncertainties in the measurements, analysts might conclude that the flows or model contain bias (systematic) error. 

Bojnowski, J. J., Groghan, R. M., Jr., and Hoffman, R. M., Direct and Indirect Material Balance Control, Chemical Engineering Progress, September 1976. 

Step 8 Solve the Equations. Many material balances can be stated in terms of simple algebraic expressions. For complex processes, matrix-theory techniques and extensive computer calculations will be needed, especially if there are a large number of equations and parameters, and/or chemical reactions and phase changes involved. 

Therefore, the sum of the component balances is the total material balance while the net rate of change of any component s mass within the control volume is the sum of the rate of mass input of that component minus the rate of mass output these can occur by any process, including chemical reaction. This last part of the dictum is important because, as we will see in Chapter 6, chemical reactions within a control volume do not create or destroy mass, they merely redistribute it among the components. In a real sense, chemical reactions can be viewed from this vantage as merely relabeling of the mass. 

General Material Balances. According to the law of conservation of mass, the total mass of an isolated system is invariant, even in the presence of chemical reactions. Thus, an overall material balance refers to a mass balance performed on the entire material (or contents) of the system. Instead, if a mass balance is made on any component (chemical compound or atomic species) involved in the process, it is termed a component (or species) material balance. The general mass balance equation has the following form, and it can be applied on any material in any process. 

The third term on the left side of the equation has significance in reactive systems only. It is used with a positive sign when material is produced as a net result of all chemical reactions a negative sign must precede this term if material is consumed by chemical reactions. The former situation corresponds to a source and the latter to a sink for the material under consideration. Since the total mass of reactants always equals the total mass of products in a chemical reaction, it is clear that the reaction (source/sink) term (R should appear explicitly in the equation for component material balances only. The overall material balance, which is equivalent to the algebraic sum of all of the component balance equations, will not contain any (R term. 

Differential and Integral Balances. Two types of material balances, differential and integral, are applied in analyzing chemical processes. The differential mass balance is valid at any instant in time, with each term representing a rate (i.e., mass per unit time). A general differential material balance may be written on any material involved in any transient process, including semibatch and unsteady-state continuous flow processes ... 

The basic differential equation for mass transfer accompanied by an nth order chemical reaction in a spherical particle is obtained by taking a material balance over a spherical shell of inner radius r and outer radius r + Sr, as shown in Figure 10.12. 

More detailed statistical analyses (chemical element balance, principal component analysis and factor analysis) demonstrate that soil contributes >50% to street dust, iron materials, concrete/cement and tire wear contribute 5-7% each, with smaller contributions from salt spray, de-icing salt and motor vehicle emissions (5,93-100). A list is given in Table VII of the main sources of the elements which contribute to street dust. 

The failure to identify the necessary authigenic silicate phases in sufficient quantities in marine sediments has led oceanographers to consider different approaches. The current models for seawater composition emphasize the dominant role played by the balance between the various inputs and outputs from the ocean. Mass balance calculations have become more important than solubility relationships in explaining oceanic chemistry. The difference between the equilibrium and mass balance points of view is not just a matter of mathematical and chemical formalism. In the equilibrium case, one would expect a very constant composition of the ocean and its sediments over geological time. In the other case, historical variations in the rates of input and removal should be reflected by changes in ocean composition and may be preserved in the sedimentary record. Models that emphasize the role of kinetic and material balance considerations are called kinetic models of seawater. This reasoning was pulled together by Broecker (1971) in a paper called "A kinetic model for the chemical composition of sea water."... 

In reactor design, we are interested in chemical reactions that transform one kind of mass into another. A material balance can be written for each component however, since chemical reactions are possible, the rate of formation of the component within the control volume must now be considered. The component balance for some substance A is... 

The general material balance of Section 1.1 contains an accumulation term that enables its use for unsteady-state reactors. This term is used to solve steady-state design problems by the method of false transients. We turn now to solving real transients. The great majority of chemical reactors are designed for steady-state operation. However, even steady-state reactors must occasionally start up and shut down. Also, an understanding of process dynamics is necessary to design the control systems needed to handle upsets and to enable operation at steady states that would otherwise be unstable. 

The application of a selective pyrolysis process to the recovery of chemicals from waste PU foam is described. The reaction conditions are controlled so that target products can be collected directly from the waste stream in high yields. Molecular beam mass spectrometry is used in small-scale experiments to analyse the reaction products in real time, enabling the effects of process parameters such as temperature, catalysts and co-reagents to be quickly screened. Fixed bed and fluidised bed reactors are used to provide products for conventional chemical analysis to determine material balances and to test the concept under larger scale conditions. Results are presented for the recycling of PU foams from vehicle seats and refrigerators. 12 refs. 

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