Mass and Energy Balance Modules

The Hydrodealkylation of Toluene

The mass and energy balance modules used in Ceng 301 can be very useful in performing preliminary analyses for many design
problems. We will demonstrate the reactor modules here since there have been some recent changes in the way they are used.
The modules shown here include:
Program(s) Description Restrictions
start403a Sets up data file for start403b. Executed in UNIX window.
start403b Puts data in Matlab arrays. Data file must exist.
Basic mass balance modules for mixing, reacting, separating and splitting
mix , react, sep ,split Inlet flows to each unit must be known.
streams.
Basic mass and energy balance on reactor. Specify inlet stream, exit state & Single exit stream with all compounds in the
reacte
temp and reaction rates. Heat needed is returned. same state.
Chemical equilibrium aid. Specify same as for reacte + the pressure.
Single exit stream. Requires data so that the
reactee Returns an error measuring the distance from equilibrium. Uses kequil &
equilibrium constant can be determined.
kvalp.
reacten Extension of reacte to allow multiple exit streams with different states. Quite general, but requires more input data.

NB: The program links give you an example of the particular program works. Keep in mind, though, that a given example is not
necessarily in this file.
The hydrodealkylation of toluene is an example that was the AIChE Contest Problem in 1967 and has been discussed by several
authors since that time. It will be used to illustrate several of the mass and energy balance modules. Two reactions are followed
in this example:

1. C7H8 + H2 -> C6H6 + CH4

2. 2 C6H6 -> C6H5C6H5 + H2

The selectivity** for production of benzene depends on the conversion of toluene. A table showing this relation was given in the
AIChE Student Contest Problem.

Selectivity of HDA Process

Selectivity 0.99 0.985 0.977 0.97 0.93
Conversion 0.50 0.600 0.700 0.75 0.85

**
Selectivity is defined as mols benzene produced per mol toluene reacted.

A Matlab function was written to give the selectivity for a given conversion. Here is a listing of the function:

>>type selHDAM

function S=selHDA(x)
% Determines the selectivity in the HDA reaction
% function S=selHDA(x)
% x is the fractional conversion of toluene
% S is the mols C6H6 produced/mols toluene converted
S=1-0.003364./(1-x).^1.596;

The form of the approximation for S vs x was suggested by Douglas, but the coefficients in it were determined with the Matlab
function: polyfit on the data: (log(1-x),log(1-S)) given in the Table.
Here is a plot comparing the program with the data in the Table.

The FORTRAN program start403a is used to create a data file that includes property data for the five compounds involved in the
process :

nb:This is one of the new programs written for ceng 301 and modified for ceng 403 in 1996.

stationnm% start403a <-- Executed in a UNIX window

Copyright 1996 Rice University
All rights reserved

Give the name to be used for your

data file. No more than 16 characters.
HDA1 <-- The name can be arbitrary and you can reuse the
The output file is called:HDA1 same name to store data in
Give the number of compounds: order to keep from
5 generating many data files.
If you want to see names, formulae or headings used in
the 301 data base, execute the FORTRAN program:
shownoh.
Give the name for compound # 1
toluene
Give the name for compound # 2
H2
Give the name for compound # 3
benzene
Give the name for compound # 4
CH4
Give the name for compound # 5
biphenyl
Give the number of reactions to set or 0 to skip.
2
Enter the coefficient for each compound in the
same order the compounds are listed.
Coefficients of reactants should be negative and
coefficients of products should be positive.
Enter the coefficients for reaction 1
C6H5CH3 H2 C6H6 CH4 C6H5C6H5
-1 -1 1 1 0 <-- The main HDA reaction
the equation is balanced <-- Look for this!
If you want to redo the equation, reply: y
<-- If the equation is balanced, it is probably OK.
Enter the coefficients for reaction 2
 C6H5CH3 H2 C6H6 CH4 C6H5C6H5
0 1 -2 0 1 <-- biphenyl from benzene side
the equation is balanced reaction
If you want to redo the equation, reply: y

If you want to set plug flow reactor parms, reply: y

<-- Not this time

We can then load the data into Matlab arrays with start403b by:

>>start403b
Copyright 1996 Rice University
All rights reserved

If you have not run the FORTRAN program start403a to

produce a data file, do so now.

How many streams will there be?10

Here are your compounds' names:
toluene
hydrogen
benzene
methane
biphenyl
Here are your reactions:
C6H5CH3 + H2 --> C6H6 + CH4
2 C6H6 --> H2 + C6H5C6H5

The problem specifications for the HDA plant include:

1. The production rate of 99.97% benzene is given as 265 lb mols/hr.

2. "Pure" toluene is to be mixed with a feed stream that is 95% H2 and 5% methane and is available at 550 psia and 100 °F.
 3. The reactor feed must have a ratio of H2 to aromatics >= 5.
4. The reactor must be operated at temperatures between 1150 °F and 1300 °F. Its pressure is set at 500 psia.

Since the stoichiometric ratio of hydrogen to toluene is 1 (neglecting the second reaction), the product from the reactor must
have a large amount of hydrogen in it. One way to handle this excess hydrogen is to separate off the light gases from the
aromatics and recycle most of the light gases. We can not recycle all the gas stream because this would cause the methane to
build up to unacceptable levels in the reactor. If it is not economical to separate the hydrogen from the methane, our only choice
is to purge some of both and to use the purge stream for fuel. Here is the way our process looks:

There are many other possible diagrams that we might examine including ones in which the heavy product is separated so that
the toluene in it could be recycled, but this will suffice for the present. The flow diagram is shown in more detail than we will
need in most of our demonstration. First, we will simply look at overall balances around the plant. Let's number the streams that
are involved in the overall balances as follows:

Stream Molar Flow Rate From To

 1 N1 H2 + CH4 Feed Mixer
2 N2 Toluene Feed Mixer
3 N3 Separator Benzene Product
4 N4 Separator Toleune + Biphenyl
5 N5 Splitter Purge Gases

Here are mass balances around the plant with the rates of the reactions specified as r1 and r2. The benzene product is specified,
so N3 is known. This assumes the product is essentially all benzene. Designate the conversion of toluene as x and its selectivity to
form benzene as S(x). Specify the fraction H2 in the purge and recycle streams as PyH2.

Table of Plant Mass Balances

Species Balance
C7H8 x*N2 = r1
C6H6 r1 - 2r2 = N3
H2 0.95N1 = PyH2*N5 + r1 - r2
CH4 0.05N1 + r1 = (1-PyH2)N5

Adding the H2 and CH4 balances gives:

N1 = N5 -r2 so 0.05N1 + r1 = (1-PyH2)(N1+r2) -> N1 = (r1-(1-PyH2)r2)/(0.95-PyH2)

The selectivity gives:
S(x) = (r1-2r2)/r1 or 1-S(x) = 2r2/r1

For given N3, x and PyH2, we can then solve for all the flows and reaction rates. First we get the reaction rates from the benzene
balance and the selectivity relation:
 r1 -(1-S(x))r1 = N3 or r1 = N3/S(x)
r2 = (1-S(x)r1/2
N2 = r1/x from the toluene balance
N1 = (r1-(1-PyH2)r2)/(0.95-PyH2)
N5 = N1 + r2
The amount of toluene in stream 4 must equal the amount that is not converted in the reactor: (1-x)N2 and the amount of
biphenyl is r2. The Matlab program: mbalHDA solves the equations for given values of conversion and H2 mol fraction in the
purge.
function [Ns,P4tol,r1,r2]=mbalHDA(x,PyH2)
% Solution of the mass balances for the HDA plant
% function [Ns,P4tol,r1,r2]=mbalHDA(x,PyH2)
% Arguments & returned variables
% x is the conversion of toluene
% PyH2 the mol fraction H2 in the purge
% Ns is the flow of the two feed and 3 product streams
% Ns(1) is the H2 + CH4 feed
% Ns(2) is the toluene feed
% Ns(3) is the benzene product
% Ns(4) is the toluene + biphenyl product
% Ns(5) is the purge rate
% P4tol is the mol fraction toluene in stream 4
% r1 is the rate of: C7H8 + H2 -> C6H6 + CH4
% r2 is the rate of: 2 C6H6 -> (C6H5)2 + H2
% Global variables used:
% PC6H6 benzene product rate
% FyH2 mol fraction of H2 in the feed gas
global PC6H6 FyH2
Sx=selHDA(x); % selectivity function
r1=PC6H6/selHDA(x);
r2=(1-Sx)*r1/2;
Ns(3)=PC6H6;
Ns(2)=r1/x;
Ns(1)=(r1-(1-PyH2)*r2)/(FyH2-PyH2);
Ns(5)=Ns(1)+r2;
N4tol=(1-x)*Ns(2);
N4bp=r2;
Ns(4)=N4tol+N4bp;
P4tol =N4tol/(N4tol+N4bp);

Here is a sample execution of the program (after using start403b to load the data in file: HDA1 so we can then
check mbalHDA with the modules.)

>>global PC6H6 FyH2

>>PC6H6=265*1000/2.2 <-- Converting the given flow to mol/hr
PC6H6 =
1.2045e+05
>>FyH2=0.95;
>>[Ns,P4tol,r1,r2]=mbalHDA(0.8,0.25) <-- x = 0.8 & PyH2=0.25
Ns =
1.0e+05 *
1.7702 1.5748 1.2045 0.3426 1.7978
P4tol =
0.9193
r1 =
1.2598e+05
r2 =
2.7650e+03

Now we can use the react module to check the values returned by mbalHDA. We set the feed streams in ns.

>>ns(1,[2 4])=Ns(1)*[0.95 0.05]; <-- Stream 1 has H2 & CH4

>>ns(2,1)=Ns(2); <-- Stream 2 is all toluene

Next we use the react (loading HDA1 set the stoichiometry) module with the rates returned by mbalHDA.
>>react([r1,r2],1:2,6)
>>showm(1:2,6,12,1)
Compound Inlet | Outlet
Stream 1 2 Total | 6
toluene 0.0 157480.8 157480.8 | 31496.2
hydrogen 168164.7 0.0 168164.7 | 44945.1
benzene 0.0 0.0 0.0 | 120454.5
methane 8850.8 0.0 8850.8 | 134835.4
biphenyl 0.0 0.0 0.0 | 2765.0
Total 177015.5 157480.8 334496.2 | 334496.2

Note that there is no need to separate stream 6 into the product streams. The gases will be purged and the excess toluene and
biphenyl will go to the liquid waste. Thus we can see that:

1. The benzene product rate is correct: 1.2045e+05

2. The mol fraction H2 in the purge is: 0.25
3. The mol fraction toluene in the heavy product is: 0.919
4. The fraction of the toluene converted is 0.8

The following table shows how much of each compound enters and leaves the plant.

Compound In Feeds In Products

Toluene N2 (1-x)N2
Hydrogen 0.95N1 PyH2*N5
Benzene 0 N3
Methane 0.05N1 (1-PyH2)N5
Biphenyl 0 r2
The results given by mbalHDA can be used to determine all flows in this table for given values of x and PyH 2. The
function mflowHDA determines these flows:

function [Nin,Nout]=mflowHDA(x,PyH2)
% Feed and product flows in the HDA plant
% function [Nin,Nout]=mflowHDA(x,PyH2)
% Arguments & returned variables
% x is the conversion of toluene
% PyH2 the mol fraction H2 in the purge
% Nin are the molar flows of all compounds into the plant
% Nout are the molar flows of all compounds out of the plant
% Global variables used:
% PC6H6 benzene production rate
% FyH2 mol fraction of H2 in the feed gas
% Order of compounds: 1) toluene, 2) hydrogen, 3) methane,
% 4) benzene, 5) biphenyl
global PC6H6 FyH2
[Ns,P4tol,r1,r2]=mbalHDA(x,PyH2);
Nin=[Ns(2) FyH2*Ns(1) 0 (1-FyH2)*Ns(1) 0];
Nout=[(1-x)*Ns(2) PyH2*Ns(5) Ns(3) (1-PyH2)*Ns(5) r2];

Here is a sample run:

>>[Nin,Nout]=mflowHDA(0.8,0.25)
Nin =
1.0e+05 *
1.5748 1.6816 0 0.0885 0
Nout =
1.0e+05 *
0.3150 0.4495 1.2045 1.3484 0.0277
The toluene and hydrogen feeds are reasonably expensive while the benzene product is (we hope) more valuable. All the
products except benzene are less valuable unless they are separated to make "pure" products. It is usual to use these other
products as fuel. Douglas gives costs that are probably out of date, but give us a basis for determining the "economic potential"
of the process. Douglas' cost have been converted to SI units and stored as $/kg of each of the compounds in this example.

The costs are stored in two arrays: CcostYP, and RcostYP. The first array holds cost data for crude compounds (such as might
be used for fuel) while the second array has data for refined compounds. Each row of each array holds data for a different
compound while the columns give the cost, year cost was found and the purity of the compound respectively. Data stored in the
second and third columns for our compounds are rough estimates since the data came from a source that would require
considerable research to find. The costs (as $/kg) in the first columns are shown next:

>>[CcostYP(:,1)';RcostYP(:,1)']'
ans =
0.0800 0.1530 <-- toluene
0.2680 1.4400 <-- hydrogen
0.0790 0.2550 <-- benzene
0.1050 NaN <-- methane
0.0770 NaN <-- biphenyl

No data is needed in this problem for refined methane or biphenyl.

We are now in a position to find the net profit from our operation. This of course is a very low level estimate since we have not
yet included very important costs such as those for equipment, utilities and labor. Those can be added as more detail about the
design is developed. We know that if the net profit is not quite high at this level of design, the project can not be worth pursuing.
Here is our first economic potential function for the HDA process:

function prof=ecop1(x,PyH2)
% prof=ecop1(x,PyH2) economic potential of HDA
% Low level economic potential accounting for the
% costs of raw materials and products
% compounds must be in the order: toluene, H2, benzene,
% methane, biphenyl
global mw CcostYP RcostYP
[Nin,Nout]=mflowHDA(x,PyH2);
crude=CcostYP(:,1)';
refin=RcostYP(:,1)';
Fin=Nin.*mw'/1000; % kg/hr
Fout=Nout.*mw'/1000; % kg/hr
buy=Fin([1 2 4])*[refin(1:2),crude(4)]';
sell=Fout*[crude(1:2),refin(3),crude(4:5)]';
prof=sell-buy;

Here is a check on the profit calculated by ecop1 using the flows generated by the react module:

Summary of ecop1 Profit Calculations - System 1

Compound Flow (mol/hr) Flow (kg/hr) Cost ($/kg) Cost ($/hr)
Toluene 157481 14510 0.153 2220
Hydrogen 168165 339 1.440 488
Methane 8851 142 0.105 15
Total 2723
Summary of ecop1 Profit Calculations - System 2
Compound Flow (mol/hr) Flow (kg/hr) Cost ($/kg) Cost ($/hr)
Toluene 31496 2902 0.080 232
Hydrogen 44945 90.6 0.268 24
Benzene 120454 9409 0.255 2399
Methane 134835 2163 0.105 227
Total 2915
This shows that the net profit will be $192/hr while the program gives:

>>ecop1(0.8,0.25)
ans =
192.5540

We can now see how the conversion influences the economics for fixed composition of the recycle stream:

>>for x=0.6:0.1:0.9
ep=[ep,ecop1(x,0.25)];
end
>>ep
ep =
-110.8313 72.6032 192.5540 187.7396

It appears that the "best" conversion would be around .8 or possibly a little higher. What if we look at the effect of the recycle
composition?

>>for y=0.2:0.1:0.9
ep1=[ep1,ecop1(0.85,y)];
end
>>ep1
ep1 =
1.0e+03 *
Columns 1 through 7
0.2481 0.1886 0.1074 -0.0098 -0.1939 -0.5254
-1.2989
Column 8
-5.1663
The economic potential continually drops with increasing mol fraction of the hydrogen in the recycle stream. If the mol fraction
is greater than about 0.45 (for a conversion of 0.85) there is no reason to operate the plant. If we set the hydrogen mol fraction
to 0, we get the maximum economic benefits:

>>ecop1(0.85,0)
ans =
329.4940
>>ecop1(0.85,0.01) <-- Even a small hydrogen loss cuts our
ans = economic potential
326.2459

Problems arise if we try to use too low a concentration of hydrogen in the recycle stream. We can see these by looking at what
happens to the recycle rate needed to meet the requirement of 5 mols hydrogen to one mol aromatics in the feed to the reactor.
Let's compare two cases both with a conversion of 0.85, in the first we set the mol fraction H2 in the recycle as 0.1 and in the
second as 0.25. Then the feeds must contain:

Case 1: PyH2=0.1

>>mflowHDA(0.85,0.1)
ans =
1.0e+05 *
1.5229 1.4015 0 0.0738 0

Let's put these flows in a table to see how we can get the recycle to meet our H2: aromatics restriction:

Molar Flows in Kg*Mols/Hr

Compound Feeds Recycle Reactor Feed
Toluene 152.29 0 152.29
 Hydrogen 140.15 0.1N6 761.45=140.15+.1N6
Methane 7.38 0.9N6 7.38+.9N6
Total 299.82 N6 299.82+N6

Thus the recycle rate must be: N6=6,213 kg mols/hr!

Case 2: PyH2=0.25

>>mflowHDA(0.85,0.25)
ans =
1.0e+05 *
1.5229 1.7110 0 0.0901 0
Molar Flows in Kg*Mols/Hr
Compound Feeds Recycle Reactor Feed
Toluene 152.29 0 152.29
Hydrogen 171.10 0.25N6 761.45=171.10+.25N6
Methane 9.01 0.75N6 9.01+.75N6
Total 332.40 N6 332.40+N6

This time the recycle rate is 2,361.4 kg mols/hr. The next table summarizes the flows and the mol fractions in the feed stream to
the reactor for the two cases.

Case 1: PyH2=0.1 Case 2:PyH2=0.25

Recycle Flow Reactor Flow Reactor Feed (mol Recycle Flow Reactor Flow Recycle Feed (mol
Comps.
(kgmol/hr) (kgmol/hr) fractions) (kgmol/hr) (kgmol/hr) fractions)
Toluene 0 152.3 0.023 0 152.3 0.057
H2 621.3 761.5 0.117 590.3 761.5 0.283
CH4 5591.7 5599.1 0.860 1771.1 1780.1 0.661
Total 6213.0 6512.9 1.000 2361.4 2693.9 1.001

It is not hard to see that as the mol fraction H2 in the recycle goes to zero the recycle rate tends to infinity. Furthermore the
concentration of the reactants in the feed to the reactor tend to zero, since the reactor feed becomes all methane. A high recycle
rate requires increased utilities for pumping, heating and cooling as well as larger piping and vessels. The lower concentration
of reactants requires a larger reactor. Thus we may save on raw material costs by lowering the amount of hydrogen in the purge
stream, but equipment and utility costs will more than offset these savings at some point.

We will pick one case to determine all the flows in our process using the mass balance modules. A conversion of 0.85 and mol
fraction H2 in the recycle of 0.25 still seem reasonable.

>>[Ns,P4tol,r1,r2]=mbalHDA(0.85,0.25)
Ns =
1.0e+05 *
1.8011 1.5229 1.2045 0.2734 1.8460
P4tol =
0.8355
r1 =
1.2945e+05
r2 =
4.4965e+03

>>ns(1,[2 4])=Ns(1)*[0.95 0.05]; <-- H2 + CH4 Feed

>>ns(2,1)=Ns(2); <-- Toluene Feed
>>ns(6,[2 4])=2361400*[0.25 0.75]; <-- Recycle
>>mix([1 2 6],7) <-- Reactor Feed
>>showm([1 2 6],7,10,1)
Compound Inlet | Outlet
 Stream 1 2 6 Total | 7
toluene 0.0 152291.3 0.0 152291.3 | 152291.3
hydrogen 171102.1 0.0 590350.0 761452.1 | 761452.1
methane 9005.4 0.0 1771050.0 1780055.4 | 1780055.4
Total 180107.5 152291.3 2361400.0 2693798.8 | 2693798.8

>>react([r1,r2],7,8) <-- Reactor outlet

>>showm(7,8,12,1)
Compound Inlet | Outlet
Stream 7 | 8
toluene 152291.3 | 22843.7
hydrogen 761452.1 | 636501.0
benzene 0.0 | 120454.5
methane 1780055.4 | 1909503.0
biphenyl 0.0 | 4496.5
Total 2693798.8 | 2693798.8

>>sep([1 0 1 0 1],8,9:10) <-- Heavy liquids to 9 and

>>showm(8,9:10,11,1) light gases to 10
Compound Inlet | Outlet
Stream 8 | 9 10 Total
toluene 22843.7 | 22843.7 0.0 22843.7
hydrogen 636501.0 | 0.0 636501.0 636501.0
benzene 120454.5 | 120454.5 0.0 120454.5
methane 1909503.0 | 0.0 1909503.0 1909503.0
biphenyl 4496.5 | 4496.5 0.0 4496.5
Total 2693798.8 | 147794.8 2546004.0 2693798.8

>>sep([0 0 1 0 0],9,3:4)
<-- Benzene product to 3
>>showm(9,3:4,11,1)
Compound Inlet | Outlet
Stream 9 | 3 4 Total
toluene 22843.7 | 0.0 22843.7 22843.7
benzene 120454.5 | 120454.5 0.0 120454.5
biphenyl 4496.5 | 0.0 4496.5 4496.5
Total 147794.8 | 120454.5 27340.2 147794.8

>>ns(6,:)./ns(10,:) <-- How much of 10 goes to the

Warning: Divide by zero recycle stream 6?
ans =
NaN 0.9275 NaN 0.9275 NaN

>>split([0.0725 0.9275],10,5:6) <-- splitting the purge and

>>showm(10,5:6,11,1) recycle streams
Compound Inlet | Outlet
Stream 10 | 5 6 Total
hydrogen 636501.0 | 46146.3 590354.7 636501.0
methane 1909503.0 | 138439.0 1771064.0 1909503.0
Total 2546004.0 | 184585.3 2361418.7 2546004.0

The reactor modules can be very helpful in seeing how to meet one more restriction. There are two main ways to operate the
reactor: isothermally or adiabatically. The first allows for more control of the process, but it requires the installation of heat
transfer equipment in the reactor. Since that can be expensive, it should be avoided if it possible to operate adiabatically. We
will use the reacte module to see what would happen if we operate in either mode. First let's look at isothermal operation. The
molar flows to the reactor are in the array ns. The temperature should be 1150 °F or 894.26K. The modules are only
approximate for low pressure where ideal gaseous behavior is valid. Thus the specified pressure will be ignored.

>>Tdeg <-- Checking the units for temperature

Tdeg =
K
>>setne('v',7,894.26,ns(7,:)) <-- Setting the reactor feed
>>reacte('v',894.26,7,8,[r1,r2]) <-- Isothermal operation
ans =
-6.3688e+06 <-- We need to remove 6.4 million kJ/hr
>>reacte('v',1000,7,8,[r1,r2]) <-- At a higher temp.
 we need to add heat.
ans =
1.3536e+07
>>r1
r1 =
1.2945e+05
>>r2
r2 =
4.4965e+03
>>ssec2([894 1000],'reacte(''v'',x,7,8,[1.2945e+05,4.4965e+03])')
ans =
928.9652 <-- The adiabatic exit temperature: = 1212.5 °F

Since the adiabatic temperature is less than 1300 °F, this should be the preferred way to design the reactor.