1 Module 10

2 Balances on Chemical Processes

3 ‫املوازانت لعمليات الكيمياوية‬
4 Duration: Three Lectures (2 Hours/ Week)
5 Instructor: Dr. AMJED AHMED
6 Ref: Richard M. Felder. Elementary Principles of Chemical Processes, 3rd edition 2005.
7

8 First Lecture
9
10 10.1 DEGREE-OF-FREEDOM ANALYSIS REVISITED
11 The degrees of freedom of a system, df, is the number of system variables whose values
12 must be specified before the remaining variables can be calculated.
13 df = Number of Variables – Number of Independent Equations
14  If df = 0 the unknown system variables can be calculated (e.g., three independent
15 equations in three unknowns).
16  If df < 0, there are more equations than variables,
17  If df > 0, (e.g., df = 2 three equations in five unknowns)number of variables must be
18 specified as part of the system definition by:
19 Design variables are externally specified
20 State variables are calculated from the system equations.
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1 EXAMPLE 10.1-1 Degree-of-Freedom Analysis of a Single Process Unit

2 A liquid mixture of n-hexane (HX) and n-heptane (HP) at a high pressure is abruptly exposed
3 ‫تمدد بشكل مفاج‬to a lower pressure. A portion ‫ جزء‬of the mixture evaporates, yielding a vapor
4 mixture relatively rich in hexane (the more volatile of the two feed components) and a
5 residual liquid mixture relatively rich in heptane. The two product streams are in equilibrium
6 at T and P; their compositions are related by Raoult’s law. Perform a df analysis on the unit.
7
8 SOLUTION

9
∗ ∗
10 Ten variables n1 , n2 , n3 , x1 , x2 , x3 , T , P , 𝑃𝐻𝑥 , and 𝑃𝐻𝑃
11 Six equations among the system:

12
13 df = 10 – 6 = 4. Four of these variables must be specified in a problem statement, a solution
14 procedure for the following sets of design variables:
15 n1, x1, T, and x3 or n2, x2, n3, and x3
16
17 1. Design variables n1, x1, T, P, and x3. For this choice of design variables, the following
18 relatively solution procedure could be used to solve for the remaining (state) variables.
 Balances on Chemical Processes 3 / 13

1
2 2. Design variables n2, x2, n3, and x3. For this choice of design variables, a relatively lengthy
3 trial and-error procedure is required to solve for the remaining variables.

4
5 Several methods can be used for the trial-and-error calculation, such as
6 𝐹(𝑇) = 𝑥2 (𝑐𝑎𝑙𝑐) − 𝑥2 (𝑠𝑝𝑒𝑐𝑖fi𝑒𝑑)
 Balances on Chemical Processes 4 / 13

1 The procedure for performing a df analysis on a multi-unit process

2 1. Draw and completely label the flowchart.
3 2. Determine the local degrees of freedom for each process unit, mixing point, and stream
4 splitting point in the process. The relations may include material balances, an energy
5 balance, equilibrium relations, and specifications of conversions, yields, selectivities, and
6 mass or mole ratios.
7 3. Determine the degrees of freedom of the total process. This quantity equals the sum of
8 the local degrees of freedom, minus the number of independent relations among process
9 variables that were not counted in step 2 (such as overall reactant conversions or
10 percentage recoveries), minus the number of ties (overcounted variables) between units.
11 ‫عدد درجات الحرية الكلية = مجموع عدد درجات الحرية للوحدات – عدد المعادالت للنظام ي‬
‫الت لم تحسب – عدد‬
12 ‫المتغيات المشيكة ر ن‬
‫بي الوحدات‬ ‫ر‬
13 EXAMPLE 10.1-1 df Analysis of a Multiple-Unit in non-reactive Processes

14
15 1. How many local degrees of freedom does each unit possess?
16 2. How many total degrees of freedom does the entire process system possess?
17
18 df analysis for unit A is six for each block. There are count nine variables (three for each
19 stream entering or leaving the unit) and three equations (mass balances on methane,
20 ethane, and ethylene).
21 The units are linked so that in the preceding analysis we have overcounted variables, the
22 three variables associated with the product stream from unit A (n3, x3, and y3) are identical
23 ‫متطابقة‬to the three associated with the feed to unit B. The analysis proceeds as follows:
24 Overall df = local df (6+6) – 0 – 3 overcounted = 9
 Balances on Chemical Processes 5 / 13

1 EXAMPLE 10.1-2 df Analysis of a Multiple-Unit Process Equipment

2 Methanol may be produced from carbon monoxide and hydrogen in the reaction

3
4 The fresh feed, (CO and H2), enters the process at a rate of 2.2 m3/s at 25 °C and 6.0 MPa
5 and combines adiabatically with a recycle stream. The combined stream is heated to 250 °C
6 and fed to the reactor. The reactor effluent emerges at the same temperature and is cooled
7 to 0 °C at P = 6.0 MPa in condenser, partially condensing the methanol product. The gas
8 leaving the condenser is saturated with methanol: 1% is taken off for process monitoring
9 purposes and the remainder is recycled. An overall CO conversion of 98% is achieved. The
10 ratio of H2 to CO is 2 mol H2/1 mol CO everywhere in the process system. Ideal gas behavior
11 may be assumed.
12 a) Carry out a df analysis for this process
13 b) Outline a manual calculation procedure to determine the compositions of all streams,
14 c) Compute the temperature after mixing point.
15 d) Compute the required heat duties for all process units,
16
17 SOLUTION

18
19

20
 Balances on Chemical Processes 6 / 13

3
4

5
6 b) The solution of the system equations
7  Calculate n0 by the ideal gas equation.
8  Calculate n3 from the specified overall CO conversion (Conversion = (no – n3)/ n0).
9  Calculate n6 by Raoult’s law at the condenser.
10  Calculate n5 from An overall carbon balance.
11  Calculate n1 and n2 by Balances on CO and CH3OH at the mixing point.
12 c)
13  Calculate Ta by an energy balance at the mixing point.
14 d)
15  Calculate Qh by An energy balance on the preheater.
16  Calculate n4 from a methanol balance on the condenser.
17  Calculate Qr and Qc by energy balances on the reactor and the condenser,
18 respectively.
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1 EXAMPLE 10.2-3 df Analysis of a Multiple-Unit in reactive Processes

2 The gas-phase dehydrogenation of isobutane to isobutene (C4H10  C4H8 + H2) is carried out
3 in a continuous reactor. A fresh feed of pure isobutane is mixed adiabatically with a recycle
4 stream containing 90 mole% isobutane and the balance isobutene, and the combined stream
5 goes to a catalytic reactor. The effluent from this process goes through a separation unit: (i)
6 one product stream containing all of the hydrogen and 1% of the isobutane leaving the
7 reactor as well as some isobutene, and (ii) the other product stream is the recycle to the
8 reactor. The single-pass isobutane conversion in the reactor is 35%. All streams shown are
9 gases. Qr is the required rate of heat transfer to the reactor and Qs is the net rate of heat
10 transfer to the separation process.
11
12 For simplicity, the symbol A will be used to denote isobutane, B denotes isobutene, and C
13 denotes hydrogen.

14
15 a) Perform a df analysis on the process.
16 b) Show that the given information is sufficient to allow the calculation of the
17 component flow rates for all streams,
18
19 SOLUTION
20 first calculate the local degrees of freedom associated with each unit, and then the net
21 degrees of freedom for the process.

22
 Balances on Chemical Processes 8 / 13

2
3

4
5 The problem can in principle be solved for all labeled variables.
6
7 b) Before planning the solution strategy, let us observe the flowchart and confirm that we
8 cannot proceed in a unit-to-unit manner without trial and error.
9 Unfortunately, we cannot solve them either, since we must first know nA1 and nA2, for which
10 we must solve the mixer equations, and we are back where we started.
11
12 The first choice. Two variables, the second one involves three variables, and the third
13 involves only one (n4). The fewer variables you have to determine by trial and error, the
14 more likely you are to succeed.
15
16 10.3 EQUATION-BASED SIMULATION
17 The problems the process engineer wants to solve fall into either of two other categories:
18 (a) Given process conditions and product stream variables, calculate feed stream variables.
19 (b) Given feed and product stream variables, calculate process conditions.
20 In both cases, iterative calculations using design specifications and convergence blocks are
21 required to solve the problems using a sequential modular program.
 Balances on Chemical Processes 9 / 13

1 EXAMPLE 10.3-1 Simulation and Design of a Two-Column Separation Process

2 A stream containing 35wt% benzene (B), 50% toluene (T), and the balance xylene (X) is fed to
3 a distillation column. The overhead product from the column contains 67.3 wt% benzene
4 and 30.6% toluene. The bottoms product is fed to a second column. The overhead product
5 from the second column contains 5.9 wt% benzene and 92.6% toluene. Of the toluene fed to
6 the process, 10% is recovered in the bottoms product from the second column, and 90.0% of
7 the xylene fed to the process is recovered in the same stream.
8 a) Perform a df analysis on the process
9 b) Outline a manual calculation procedure to determine the compositions of all streams.
10 c) Construct a set of n equations in the n unknown stream variables identified.
11
12 SOLUTION Basis: 100 kg Feed

13

14
 Balances on Chemical Processes 10 / 13

1 b) A manual solution is easily outlined. The specified recoveries of toluene and xylene in the
2 bottoms from the second column allow the immediate determination of n7 and n8, leaving
3 three unknowns n1, n5, and n6 in the overall process system. Overall toluene and xylene
4 balances provide two equations in two unknowns n1 and n5 and an overall mass balance
5 then yields n6. Finally, benzene, toluene, and xylene balances on either Column 1 or Column
6 2 yield solutions for n2, n3, and n4.
7
8 c) The system equations are given below.
9

10
11
12 We thus have eight equations in eight unknowns. The equations may easily be entered into
13 an equation-solving program and solved to obtain:
14
15 n1 = 48.1, n2 = 2.65, n3 = 35.3, n4 = 14.0, n5 = 32.7, n6 = 0.72, n7 = 5.0, and n8 = 14.0.
 Balances on Chemical Processes 11 / 13

1 EXAMPLE 10.3-2
2 Ethane is dehydrogenated to ethylene and acetylene in the following pair of catalytic
3 reactions:

4
5 The reactions take place at 977 °C and 1 atm and proceed to a point such that the product
6 gas composition satisfies the following equilibrium conditions:

7
8 Where y is mole fraction. The product gas goes to a complex separation process that
9 separates 95% of the unreacted ethane from the ethylene, acetylene, and hydrogen and
10 recycles the separated ethane to the reactor.
11 a) Perform a df analysis on this process,
12 b) Set up the equations for all unknown stream variables,
13 c) Outline a method of solution.
14
15 SOLUTION Basis: 100 mol Ethane Fed to the Reactor

16
17 a) The df analysis proceeds in the customary manner.

18
 Balances on Chemical Processes 12 / 13

1
2
3 b) The system equations are as follows.

4
5 Reactor: We will use the extent of reaction method for the reactor analysis,

6
7 The mole fraction of the ith component in the reactor effluent is ni/ntotal. The mole fractions
8 of all four species can be expressed in terms of 1 and 2 using Equations 2 through 6, and the
9 resulting expressions can be substituted into the given equilibrium relations to yield the
10 following equations:

11
12
13 c) Examining the 10 equations, we see that two are nonlinear (Equations 7 and 8) and the
14 remainder are linear. The following procedure involving no more than two simultaneous
15 equations could be used:
 Balances on Chemical Processes 13 / 13

1
2 The only problem that remains is the simultaneous solution of Equations 7 and 8. We first
3 rewrite each of the two equations in the form f(ξ1, ξ2) = 0 by multiplying through by the
4 denominators of the left sides and bringing all terms to the left of the equal sign.
5 Equation 7 becomes

6
7 From equation 8

8
9 These two equations may be solved simultaneously using an equation-solving program or a
10 numerical procedure like the Newton–Raphson algorithm.
11 The solution is ξ1 = 83.06 mol, ξ2 = 6.127 mol.
12 Then n1 = 10.81 mol, n2 = 83.06 mol, n3 = 6.127 mol, n4 = 95.32 mol, n5 = 0.5405 mol, n6 =
13 10.27 mol, n0 = 89.73 mol.