Course Module

Petroleum Process Operations

Material Balances
PROP 6020
023-11-93-10

G7601164

MacPhail School of Energy

Revised: July 2007

www.sait.ca

Material Balances
Rationale
Why is it important for you to learn this material? The efficient movement of material through chemical and physical processes is critical. Determining both efficiency and bulk movement of material is determined using Material Balance calculations. In this section, the student will learn how to; solve steady-state material balance problems for processes which do not involve chemical reactions, to solve material balance equations, write mathematical equations representing overall component balances, and to determine stream flow rates and/or compositions.

Learning Outcome
When you complete this module you will be able to . Solve steady-state material balance problems for processes that do not involve chemical reactions.

Learning Objectives
Here is what you will be able to do when you complete each objective. 1. State the theoretical principles of material balance. 2. When given a written process description, solve a typical material balance problem using a systematic set of procedures. 3. Solve material balance equations to determine stream flow rates and/or compositions.

Introduction
Material balances are fundamental engineering techniques used in design, trouble shooting, process optimization, and plant operation. Material balance problems can vary in complexity, from simple ones which can be easily solved by hand, to extremely complex problems requiring computer-based solutions. Even though the complexity changes for different problems, the principles that form the basis for solving them remain constant. An understanding of these principles, and the uses of material balances, is useful in many aspects of engineering. In this module, an understanding of these principles will be developed by solving several material balance problems.
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OBJECTIVE ONE
When you complete this objective you will be able to State the theoretical principles of material balance.

Learning Material
MATERIAL BALANCE PRINCIPLES It is accurate to say that mass is conserved in all types of processes, except in those that involve nuclear transformations. This principle is sometimes called the Law of Conservation of Matter, and forms the basis for material balances. Some common processes appear, at first glance, to violate this principle. For example, if a fuel such as wood or coal is burned, the mass of ash left behind is certainly less that the mass of fuel originally present. However, a more complete analysis will show that the mass of the combustion gases produced plus the residual ash will equal the mass of fuel burned plus the air which reacted. In fact, mass is conserved. There are no exceptions to this principle other than nuclear processes. The implications and uses of this principle in engineering calculations are significant. In any industrial plant or process which is operating at steady state conditions, the total mass entering the process must equal the total mass leaving the process. (Steady state implies that the levels in the tanks or vessels are not rising or falling.) The principle that mass in must equal mass out can be used to: Check for leaks in equipment. Verify the accuracy of flow meters. Perform plant design calculations. Account for or estimate losses. Calculate operational requirements. Note that the mass entering a process must equal the mass leaving. The same cannot be said about volume. If one cubic metre of gas enters a compressor, the volume of gas leaving will not be one cubic metre, because of changes in pressure and temperature. Sometimes, when a problem involves dilute solutions, volume entering may approximately equal volume leaving. While the use of balances based on volume may occasionally be valid, it is always correct, and therefore safer, to use balances based on conservation of mass. 2

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The material balances considered in this module will deal with processes which do not involve chemical reactions. In these cases, it is valid to assume that the moles of material entering a process equal the moles of material leaving, and this can be used as the basis for setting up balances. Most of the problems in this module will be based on conservation of mass only. Introductory Example: Consider the following problem. Concentrated caustic soda (NaOH) is shipped by rail cars to many plants in Alberta. Fifty-five per cent by weight NaOH is a typical strength of the concentrated solution. The other forty-five per cent is water. Frequently, the concentrated caustic soda solution must be diluted by the addition of more water before it can be used in the process. Assuming the concentrated solution is diluted to a strength of 12% by mass, the process could be represented by Fig. 1.

Figure 1 Block Flow Diagram SAIT 2009

In Fig. 1, if the mass of concentrated solution is designated as A, the mass of water added as B, and the mass of dilute solution produced as C, then overall and component balances can be written. Overall Balance Total Mass In or A + B = C Eqn. 2 = Total Mass Out Eqn. 1

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The balances represented by Eqns.1 and 2 are referred to as overall balances, because they are based on the principle that the total mass entering must equal the total mass leaving. In this problem, where water is simply added to a strong solution of NaOH, it is evident that no NaOH is being made when this happens. In the end, there will be more kilograms of dilute solution than concentrated solution, but there will not be more pure NaOH. This principle is the basis for a second type of balance, called a component balance. Component Balance The component balance equation states that the kilograms of pure NaOH in Stream A plus the kilograms of pure NaOH in Stream B (obviously 0) must equal the kilograms of pure NaOH in Stream C. Since the original problem stated that the concentrated solution was 55% NaOH by mass, the mass of pure NaOH in this stream will be 0.55 x A. Similarly, the mass of NaOH in the water stream is 0.0 x B, and the mass of pure NaOH in the dilute stream is 0.12 x C. The fact that the mass of pure NaOH entering must equal the mass of pure NaOH leaving, can be represented mathematically as (0.55 x A) + (0.0 x B) = (0.12 x C) Eqn. 3

If Eqns. 2 and 3 are analysed, it can be seen that there are 3 unknowns and 2 independent equations. Therefore, as soon as one of the unknowns is specified or assumed, values for the other two can be calculated. As an example, determine the amount of water that must be added to dilute 1000 kilograms of concentrated (55% by mass) NaOH solution to a strength of 12% by mass. That is,

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Solution: A B C = = = mass of concentrated solution, 1000 kg mass of water added, which is unknown mass of dilute solution produced, which is unknown

Component Balance Pure NaOH in must equal pure NaOH out, so: 0.55A (0.55 x 1000 kg) C C Overall Balance Since total mass in must equal total mass out: A + B 1000 kg + B B B Conclusion 3583 kg of water must be added to 1000 kg of concentrated, 55%-by-mass NaOH solution, to produce 4583 kg of dilute, 12%-by-mass NaOH solution. = = = = C 4583 kg 4583 kg - 1000 kg 3583 kg (Ans.) = = = = 0.12C 0.12C 550 kg/0.12 4583 kg

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OBJECTIVE TWO
When you complete this objective you will be able to When given a written process description, solve a typical material balance problem using a systematic set of procedures.

Learning Material
MATERIAL BALANCE PROCEDURES The preceding example is a simple but typical type of material balance problem. As the number of streams involved increases, the complexity of material balance problems will increase, even though the fundamental principles remain the same. The following procedural steps are presented to assist the student with the development of logical, coherent solutions for material balance problems: 1. Carefully read over the problem (several times if necessary) to gain an understanding of the information presented. 2. Draw a block flow diagram to represent the process. 3. Clearly identify where the balance is being done by drawing a boundary around that portion of the process. 4. Identify all streams that enter and leave; that is, those streams that cut the boundary. 5. Place all unknown information (flow rates and compositions) on the diagram. 6. Identify all unknown streams. If letters are used to represent unknown stream variables, clearly state the relationship between the letter and the unknown. 7. Choose a basis for the solution. Typical choices for a basis are: a) A unit of time (second, minute, or hour). b) A specified amount of feed (e.g., 100 kg of feed). c) A specified amount of one product. 8. Write mathematical equations representing the overall and component balances. Remember, if N represents the number of unknowns, then N independent equations must be written. 9. Solve the mathematical equations to determine unknown flowrates and compositions. 10. Review your answer to see if it seems reasonable. 6
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EXAMPLES OF MATERIAL BALANCE PROBLEMS Example 1: A solution of methanol and water is fed to a distillation tower. Two products are withdrawn from the tower. The composition of the stream leaving the top of the tower is 97% methanol and 3% water. The composition of the stream leaving the bottom of the tower is 95% water and 5% methanol. Assuming that the feed stream entering the tower is 20% methanol and 80% water, and the flow of feed is 100 kg/min, calculate the flow rates of top and bottom products. All given compositions are mass per cent. Solution: Draw the block flow diagram as shown as Fig. 3.

Figure 3 Distillation Tower SAIT 2009

T = the flow rate of the top product B = the flow rate of the bottom product Basis Since the feed flow rate is given in kilograms per minute, the simplest solution will involve calculating both top and bottom flow rates in kilograms per minute. It is equally correct to work with units of mass flow as with just units of mass when performing a material balance. Overall Balance Total mass entering
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Total mass leaving 7

100 kg/min Component Balance

T + B

Eqn. 1

The distillation process simply separates methanol from water; it does not create any additional methanol or water. Therefore, it is correct to say that: Mass of methanol entering = Mass of methanol leaving Mass of methanol in feed = Mass of methanol + Mass of methanol in feed in top product in bottom product

Stated Mathematically 100 kg /min x 0.2 20 kg/min = = T x 0.97 + B x 0.05 0.97T + 0.05B Eqn. 2

It would be possible to write a similar balance based on water, but mathematically it is not necessary. There are two unknowns and two independent equations, so a solution is possible. Rearrange Eqn. 1: T = 100 kg/min - B

Substitute for T in Eqn. 2: 20 kg/min 20 kg/min -77 kg/min B = = = = 0.97 x (100 kg/min - B) + 0.05B 97 kg/min - 0.97B + 0.05B -0.92B 83.7 kg/min (Ans.)

Substitute for B in Eqn. 1 to determine that: T T = = 100 kg/min - 83.7 kg/min 16.3 kg/min (Ans.)

The flow rate of the bottom product is 83.7 kilograms per minute and the flow rate of the top product is 16.3 kilograms per minute.

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OBJECTIVE THREE
When you complete this objective you will be able to Solve material balance equations to determine stream flow rates and/or compositions.

Learning Material
ADDITIONAL EXAMPLES INVOLVING FLOWRATES Example 2: A flow meter on a natural gas line reads 15 000 kg/min. To check the accuracy of this flow meter, ammonia is injected into the gas at a flow rate of 75 kg/min. Prior to the injection point, the concentration of ammonia in the gas stream is 0.02% by mass. After the injection point, the concentration of the ammonia is 0.4% by mass. Use this information to determine whether or not the flow meter is accurate. Solution: Draw the pipeline block flow diagram as shown as Fig. 4.

Figure 4 Pipeline Flow SAIT 2009

X Y

= =

total mass flow prior to the injection of ammonia total mass flow rate after the injection of ammonia

Overall Balance X + 75 kg/min Ammonia Balance 0.0002 X + 75 kg/min = 0.004Y Eqn. 2 = Y Eqn. 1

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There are two unknowns and two equations, so a solution is possible. Use Eqn. 1 to substitute for Y in Eqn. 2 0.0002X + 75 kg/min 0.0002X + 75 kg/min -0.0038X X This number should be rounded to X = = = = = 0.004(X + 75 kg/min) 0.004X + 0.3 kg/min -74.7 kg/min 19 658 kg/min 20 000 kg/min (Ans.)

Since the calculated value of the flow rate is 20 000 kg/min and the metered value is 15 000 kg/min, the calculations do not verify the accuracy of the meter. In practice, care must be taken to insure that the discrepancy is not due to inaccurate measurements of the ammonia concentration. Example 3: A mixture of ethane, propane, and butane is separated into nearly pure components by a series of distillation towers, as shown in Fig. 5. Use the information provided on the diagram to calculate the following: 1. What fraction of the feed stream does each product stream represent? 2. What is the flow rate of the stream leaving the bottom of the first tower and entering the second?

Figure 5 SAIT 2009

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Distillation Towers Solution, Part 1: E P B F Basis Since the question asks what fraction of the feed appears in each product stream, a convenient basis is to assume there are 100 kg of feed. Choosing a different basis is not incorrect; it is simply a matter of choosing a basis that is convenient. Overall Balance The overall balance equation states that the mass of the feed must equal the mass of the three product streams. Mathematically 100 kg Note: = E + P + B Eqn. 1 = = = = the total mass of the first overhead stream. the total mass of the second overhead stream. the total mass of the second bottoms stream. the total mass of the first bottoms stream.

Stream F does not appear in this balance since it does not enter or leave the process.

Component Balance Since there are three components, it is possible to write three component balances. To solve for the three product streams, only three independent equations are required, so an overall balance and a balance based on any two components will suffice. Ethane Balance Ethane in feed (100 kg) x 0.25 25 kg E = = = = Ethane out in product streams E x 0.98 0.98E 25.51 kg Eqn. 2

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Propane Balance Propane in Feed (100 kg) x 0.45 45 kg Butane Balance Butane in Feed (100 kg) x 0.30 30 kg = Butane in Stream E (E x 0.0) 0.05P + Butane in Stream P (P x 0.05) 0.97B + Butane in Stream B (B x 0.97) Eqn. 4 = Propane in Stream E (E x 0.02) + Propane in Stream P (P x 0.95) + Propane in Stream B (B x 0.03)

0.02E

0.95P

0.03B

Eqn. 3

= =

+ +

At this point there are three equations and two unknowns. Any combination of the equations can be used to calculate the values for P and B. Substituting the value of 25.51 kg for E in Eqn. 3 gives: 45 kg 44.48 kg = = 0.02(25.51 kg) + 0.95P + 0.03B 0.95P + 0.03B Eqn. 5

Rearrange Eqn. 4 to obtain an expression to substitute for P in Eqn. 5: 0.05P P Substituting 44.48 kg 44.8 kg -525.2 kg B = = = = 0.95(600 kg - 19.4B) + 0.03B 570 kg - 18.43B + 0.03B -18.40B 28.54 kg = = 30 kg - 0.97B 600 kg - 19.4B

Now that values for E and B are known, the value of P can be found by substituting into Eqn. 1, 3, or 4. 12
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Substituting into Eqn. 1 gives: 100 kg P Therefore: Stream E Stream P Stream B = = = 25.51 kg (Ans.) 45.95 kg (Ans.) 28.54 kg (Ans.) = = 25.51 kg + P + 28.54 kg 45.95 kg

Note that the equations could have been combined in several different ways to solve for these values. Conclusion The first overhead stream is 25.51% of the feed. The second overhead is 45.94% of the feed and the bottoms are 28.55% of the feed. Solution Part 2: Overall Balance Imagine a boundary line drawn around Still #1. The feed stream enters, while streams E and F leave. Therefore an overall balance around Still #1 can be written as: 100 kg = E + F

Since E is already known to be 25.51 kg, F can be readily calculated: F F Conclusion Based on a feed amount of 100 kg, the stream flowing out of the bottom of Still #1 and feeding into Still #2 is 74.49 kg/100 kg of feed. The student may wish to determine the composition of Stream F by setting up component balances. By inspection, it can be seen that this stream contains no ethane. (If ethane were present, one of the product streams from Still #2 would contain ethane.) Calculations will show that the composition of Stream F is 59.7% propane and 40.3% butane.
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= =

100 kg - 25.51 kg 74.49 kg (Ans.)

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Module Self-Test
Directions: Answer the following questions. Compare your answers to the enclosed answer key. If you disagree with any of the answers, review learning activities and/or check with your instructor. If no problems arise, continue on to the next objective or next examination.

1. In a pulp mill, wet pulp enters a dryer with a moisture content of 48%. The other 52% is dry fibre. As it passes through the dryer, water is evaporated. The moisture content of the material leaving the dryer is 12%. If 1000 kg (in total) enter the dryer: (a) (b) how many kilograms of water are evaporated? how many kilograms of dried pulp are produced?

2. How much water must be added to 1000 L of concentrated NaOH solution to dilute the solution to 9% NaOH by mass? The relative density of the concentrated solution is 1.25 and the concentrated solution is 40% by mass NaOH. Hint: The first step is to calculate the total mass of the concentrated solution. 3. A distillation tower takes a mixture which is 70% ethane and 30% propane on a mass basis. This mixture is distilled to produce a top product which is 97% ethane and 3% propane. The bottom product is 89% propane and 11% ethane. (All analyses are mass %.) For 100 kg of feed entering the tower, calculate the amount of top and bottom product. 4. Oil and water are separated in a two phase separator. The information that is known about the flows is shown in the following table. Use this information to calculate the flow rate of the waste water stream and the feed stream. Express the answer in kg/min.
Feed Stream Mass % Oil Mass % water Flow rate 90% 10% unknown Waste Water Stream 1% 99% unknown Oil Stream 99% 1% 10 000 kg/h

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Module Self-Test Answers

1. (a) (b) 409 kg 591 kg

2. 4306 kg 3. 68.6 kg of top product and 31.4 kg of bottom product 4. Waste water = 1011 kg Feed = 11 011 kg

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Assignment
1. If 185 kg of a solution which is 10% H2SO4 is mixed with 110 kg of a solution which is 88% H2SO4, what is the strength of the resulting solution? All compositions are on a mass basis. 2. A tank contains 5000 L of solution which is 30% HCl on a mass basis. The specific gravity of this solution is 1.18. Calculate the amount of water that must be added to the tank to dilute the tank contents to17% HCl on a mass basis. 3. Feed to a distillation tower is 20% ethane and 80% propane on a mass basis. The feed flow rate is 200 kg/min. The bottom product flow rate is 155 kg/min and the bottom product is 93% propane. Calculate the flow rate and the composition of the top product. 4. In a plant, one stream is 10% propane, 70% butane, and 20% pentane. A second stream is 70% propane and 30% butane. If 500 kg of the first stream is blended with 300 kg of the second stream, what is the composition of the resulting stream? All compositions are on a mass basis. 5. The following data are from a distillation column. Does the data appear to be accurate? Show calculations to support your conclusion. Verify that both the flow rates and the compositions are correct by doing an overall and a component balance.
Flow Rate (g/min) Feed Top Product Bottom Product 1500 204 1297 % Alcohol 12% 98% 4%

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Course Module

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