MATERIAL BALANCE

Mass balance or material balance is the expression of the conservation of mass that involves accounting of materials in a process. This age old mass balance concept is useful for assessing a process and sometimes improving management practices including waste reduction, on site tracking of toxic chemicals and transportation into and out of a facility. Moreover, material balance over a process helps to check performance against design, instrument calibration and to identify the source of material loss. It also helps to extend often the limited data available from the plant instrumentation. Therefore, a good understanding of material balance is necessary.

Basic Principle of a Material Balance

In its simplest form, a material balance for any production system is drawn up according to the following principle: Material and Energy Inputs = Products + Waste Material inputs includes raw material, chemicals, energy etc. Energy includes fuel, electricity etc. Products include final products from the factory as well as by-products. Waste includes effluents, air emissions, solid wastes, waste heat, off-spec products. Einstein showed that mass and energy are equivalent. Energy can be converted into mass and mass into energy. The loss of mass associated with the production of energy is significant in nuclear reactions. In processes of nuclear fission and condensation the law of conservation of mass becomes invalid, but in ordinary industrial processes mass balance is highly practiced and it is accepted that energy and matter are to be separately conserved. The conservation of mass can be written as: Rate of flow of reactant into volume element = Rate of flow of reactant out of volume element + Rate of reactant removal by reaction within volume element + Rate of accumulation of reactant within volume element. Material balance is carried over a certain element of volume. In steady state process i.e. continuous process, the accumulation will be zero. If there is no chemical reaction the steady state balance reduces to: Rate of flow of reactant into volume element = Rate of flow of reactant out of volume element. A mass balance can be written for individual elements, compounds and for total materials. Direct measurements of quantity of components of both entering and leaving streams in a process during a given time interval needs no calculation. Calculation of material balance is indispensable when direct measurement of one or more components is not possible. The measurements require knowledge of conservation of mass and of the standard units for expressing mass data, composition, concentration, flow rate of flowing streams in a process. If there is any change of physical or chemical properties of flowing streams, that must be accountable. Appropriate judgment must be exercised in selecting the methods for sampling, analysis and in choosing the frequency and duration of data acquisition of mass flows within a process.

Gross deviation from mass balance indicates that errors have been made in sampling and quantifying one or more mass balance components or else it needs some relevant information. So, precise evaluation is needed. In a mass balance operation, all chemical inputs to a manufacturing process and outputs from it and accumulations within are first identified and the masses are measured. The mass of inputs should be equal or closely approximate the mass of outputs plus accumulations.

MATERIAL BALANCE Material balance is a basic inventory tool, which allows for the quantitative assessment of material inputs and outputs. The basis of the material balance for a process-based environmental management program is the development of a process flow diagram. Material balance establishes the major inflows and outflows and highlights any discrepancies in a quantitative manner. Exercise of Material Balance helps to carry out comparison with norms by working out specific consumption / production Material Balance also serves as a predictive tool to speculate on outputs for changed inputs or improved processes. Discrepancies once identified leads to understanding of problems and causes. Material balance carried out exclusively for energy is called Energy Balance Material balance focused on toxic materials usage is called Toxic Release Inventory (TRI) Inputs to a process or a unit operation may include raw materials, chemicals, water, air and energy. Outputs include primary product; by-products; rejects; wastewater; gaseous wastes; liquid and solid wastes which need to be stored and/or sent off-site for disposal; and reusable wastes.

Considerations in Developing Material Balance:

Material Balance need not be excessively accurate (to the order of 99%). It is difficult to achieve high accuracies when operations and processes are complicated.

 Material Balance within the tolerance range of 10% should generally be acceptable. However, if the tie compound for material balance is of a hazardous nature then, a higher order of accuracy should be targeted.

Figure: Schematic representation of a material balance sheet.

Doing a Material Balance

Determining inputs Include raw materials, chemicals, water, energy, etc. for the process/ operation. Measurements should be taken for an appropriate length of time so as to ensure that the results are representative. Averages should be taken wherever necessary and appropriate. Existing levels of material recycling should not be missed. They should be incorporated while balancing. Quantifying outputs Outputs consist of products, by-products and wastes. Attention should be paid to off-spec products and reprocessing sequences. Selection of tie compounds Suitable and representative tie compounds should be selected for preparing the material balance. Preparing a preliminary material balance Based on the inputs and the outputs, a preliminary balance should be constructed. Discrepancies should be calculated and, wherever in doubt, measurements or analysis should be repeated to refine the material balance. Refining a Material Balance The preliminary material balance should be improved by verifying the collected data during site inspections and by brainstorming.

Preparation of a preliminary material balance:

A material balance is designed to provide better understanding of the inputs and outputs, especially waste, of a unit operation such that areas where information is inaccurate or lacking can be identified. The initial balance should be considered as a rough assessment that must be further refined and improved. The units of measurement should be standardized (liter, ton or kilogram) on a per day, per year, or per batch basis. The measured values in standard units should be summarized by reference to the process flow diagram. It may be necessary to modify the process flow diagram following the in depth study of the plant. It is highly desirable to carry out a water balance for all water inputs and outputs to and from unit operations, because water imbalances may indicate underlying problems such as leaks or spills. Similarly, a detailed material balance should be carried out for important tie compound, as agreed upon by the audit team during the planning phase.

Steps in Developing a Material Balance

1. Determining Inputs: Recording raw material procurement, water and energy usage, 2. Quantifying Outputs: Accounting for wastewater, gaseous emissions, solid wastes, energy 3. Selecting a Tie compound 4. Preparing a preliminary material balance 5. Evaluating and refining material balance

The following stepbystep procedure helps to get efficient solution of material balance problems: 1. Draw a block diagram of the process to show significant steps by flow sheet diagram. 2. List all the available data. Indicate known quantities of the parameters on the block diagram. 3. List all the information. 4. Decide the system boundaries. 5. Write out all the chemical reactions involved for the main products and byproducts. 6. Note any other constraints if any, like azeotropes, phase equilibria, tie substances. 7. Check the number of conservation equations that can be written and compared with the number of unknowns. Decide the basis of calculation. The order of steps may vary according to need of the problem.

EXCESS REAGENT
In most chemical reactions carried out in industry, the components are seldom fed to the reactor in exact stoichiometric proportions. A reagent may be supplied in excess of the amounts theoretically required for combination with the others in order to maximize the use of an expensive reagent or to ensure complete reaction of a reagent. As a result, the products contain some of the unreacted reactants. The amount of desired compound is determined by the amount of limiting reactant.

The percentage excess of any reactant is defined as the percentage ratio of the excess to the amount theoretically required by the stoichiometric equation for combination with the limiting reactant. So the 'Excess' refers to limiting reagent. The percentage excess reagent is expressed by the following:

Complete reaction of the limiting material may not be achieved even in the presence of excess reagent. It happens due to insufficient time or opportunity for completion to the theoretically possible equilibrium. The degree of completion of a reaction is ordinarily expressed as the percentage of the limiting reacting material, which is converted or decomposed into other products. In case of 100% completion, outlet stream contains products and excess reactant. CONVERSION AND YIELD Conversion refers to the reactants and yield refers to the products formed. Conversion is a measure of the fraction of the reagent that converts due to reaction. Conversion is expressed by the following:

This definition indicates the total conversion of the particular reagent to all products. The conversion of a particular reagent is often less than 100 percent in order to minimize byproduct formation. If the conversion of a valuable reagent in a reaction process is appreciably less than 100 percent, the unreacted material is recycled. Yield is a measure of the performance of a reactor or plant. Yield should be defined on clearly stated basis.

Stoichiometric factor =Stoichiometric mole of reagent required per mol of product produced. 'Plant yield' is a measure of the overall performance of the plant and includes all chemical and physical losses.

When more than one reagent is used or product produced it is essential that the product and the reagent to which the yield value refers are clearly stated.

TIE-SUBSTANCES
A compound that goes directly from an input stream to an output stream without any chemical change is called a tie-substance. It is normally very useful in solving problems. It forms a tie between an input stream and an output stream. Such a material comes in to the process in just one stream and leaves unchanged in only one stream. E.g. when oxygen is needed for a reaction to take place in most cases it is supplied in the form of air. As air contains nitrogen (we will ignore argon and CO2), we must take into consideration the associated nitrogen in air. The composition of air can be taken as 79 mol% (vol%) N2 and 21 mol% O2

If the O2 input is 7.5 kmol, then N2 input = 7.5 * 79/21 = 28.2 kmol Since the nitrogen does not react, the mass balance says that what went in should come out. Therefore nitrogen output must also be 28.2 kmol. Such a material may be inert by nature some times. They must be considered before material balance where no specific chemical reaction is observed in unit operations. E.g. 1. Continuous salt solution concentrator Salt in = salt out 2. Ash in coal furnace. Tie compounds could be specific to the industry. They should be a measure of economic or environmental importance. E.g. 1. Water in textile industry 2. Heavy metals in electroplating industry A tie compound is the parameter or substance for which the material balance is established around a unit operation or process. Selection of an appropriate tie compound for checking material balance is an important step.

Estimation Procedure
In material balance, it is not always necessary to carry out measurements of inputs and outputs. Instead estimation procedures could be used as shown in the example given below in this handout.

Criteria for selecting tie compounds:

an expensive raw material/intermediate; material common in most processing stages; a substance of hazardous nature; a substance/compound easy to measure/estimate. A simple example of a tie compound is the water added to account for most wet operations. In practical situations, more specific tie compounds, e.g., nickel or zinc in electroplating shops or dyestuff in textile processing, would be ideal. Another good example is the chromium in leather tanning. Chemical oxygen demand (COD), is another very useful tie parameter which sharpens the material balance exercise, especially to link the production areas with the effluent treatment plant. Contributions of each process department in terms of total COD load in kg/day; knowing the volume of wastewater and its COD discharged by each department; and cross-checking it with the COD load observed at the treatment facilities can provide a good check on the data. In addition to water, and chemicals, etc., energy is an important tie compound, particularly for energy intensive and process sectors such as iron and steel, coke oven, textile, and pulp and paper.

ENERGY BALANCE
An energy balance may be defined as a quantitative account of the input and output forms of energy in a production process. In addition to water, and chemicals, etc., energy is an important tie compound, particularly for energy intensive and process sectors such as iron and steel, coke oven, textile, and pulp and paper. Quantities of various forms of energy input, such as fuel, steam, electricity for the plant/unit operation, would then need to be measured/completed. Energy inputs to a process or a unit operation may be in the

form of steam, hot water, electricity etc. The fuel sources to generate the heat are also included in the inputs. The output is to be quantified in terms of the enthalpy of the products, wastewater (process, condensate and cooling) and any energy losses, such as steam leakage. Energy balance is a mathematical or numerical expression of 'Conservation of energy' (also called first law of thermodynamics). Energy balance and mass balance are encountered often in the problems related to process design and operation. Principle of conservation of energy states that energy is indestructible, but can be transformed to other forms of energy and the total amount of energy entering any system must be exactly equal to that of leaving plus any accumulation within this system. Energy out = Energy in + generation consumption accumulation For steady state process the accumulation of both mass and energy will be zero. In mass balance, the total mass flow into a process unit is generally equal to the flow out at the steadystate except in biomass formation within a bioreactor where generation is concerned. In energy balance, the total enthalpy of the outlet streams will not be equal to that of the inlet streams if energy is generated (exothermic) or consumed (endothermic). Energy balance is carried out to know the energy needed in heating / cooling and supplying power in a process. 'Energy balance' exhibits a pattern of usage and suggests areas for conservation and savings. Energy can exist in many forms making 'energy balance' more complex than mass balance, such as potential energy, kinetic energy, flow energy, heating energy, mechanical energy, electrical energy etc. Total energy is conserved as per the law of conservation of energy. Energy and material balances are carried out, not only for the main process, but also for the various equipment and utilities that enable production.

ENERGY BALANCE