Hydrodealkylation of Toluene

Project report submitted:

For

Applied Process Engineering-IV (CH305G)

By

Neerav Sreekumar (CH22B025)

Raghav Khandelwal (CH22B030)

Rajan Raj (CH22B031)

Satyam Kumar Singh (CH22B035)

DEPARTMENT OF CHEMICAL ENGINEERING

INDIAN INSTITUTE OF TECHNOLOGY TIRUPATI

1
 TABLE OF CONTENTS
1. Introduction ------------------------------------------------------------------- 3

2. Process Description ---------------------------------------------------------- 3

3. Stream Table Development ------------------------------------------------- 5

4. Reactor Design and Thermodynamics ----------------------------------- 9

5. Flash component analysis --------------------------------------------------- 11

6. Heat Exchanger Design ----------------------------------------------------- 13

7. Multicomponent distillation using FUG & Kirkbride------------------- 15

8. McCabe-Thiele Method ----------------------------------------------------- 20

9. Conclusions ------------------------------------------------------------------ 23

10. References and citations ---------------------------------------------------- 23

11. Appendix ---------------------------------------------------------------------- 24

2
1. INTRODUCTION

Hydrodealkylation of Toluene (HDA Process)

The hydrodealkylation of toluene (HDA) is a process used to produce benzene, where methane

and diphenyl are also produced as byproducts. Hydrodealkylation is a chemical process in

which an aromatic hydrocarbon, like Toluene, reacts with Hydrogen gas, forming a less

complex aromatic hydrocarbon without any functional groups.

2. PROCESS DESCRIPTION

In the HDA process, fresh toluene (pure) and a mixture of 95% hydrogen and 5% methane are

mixed with recycled toluene and hydrogen (Figure 1). This reactant mixture is first preheated

in a feed-effluent heat exchanger (FEHE) using the reactor effluent stream and then to the

reaction temperature in a furnace before being fed to an adiabatic plug-flow reactor.

A primary reaction and a side reaction take place in the reactor as follows:

𝐶7 𝐻8 + 𝐻2 → 𝐶6 𝐻6 +𝐶𝐻4 (1)

2𝐶6 𝐻6 ↔ 𝐶12 𝐻10 + 𝐻2 (2)

➢ The reactor effluent is quenched by a portion of the recycle separator liquid flow to prevent

coking and further cooled in the FEHE and cooler before being fed to the vapor-liquid

separator. Part of the vapour containing unconverted hydrogen and methane is purged to

avoid the accumulation of methane within the process while the remainder is compressed

and recycled to the process. The liquid from the separator is processed in the separation

section, which consists of three distillation columns. The stabiliser column removes tiny

amounts of hydrogen and methane in the overhead product, and the benzene column takes

off the benzene product in the overhead.

➢ The range of temperatures where the homogeneous reactions occur is 600 ℃ , below which

the reaction rate is too slow, to 700 ℃ , above which a considerable amount of

3
 hydrocracking occurs, and at a pressure of roughly 35 bar. In order to avoid coking, there

must be an excess of hydrogen—a 5:1 ratio.

➢ Quenching is the process of rapidly cooling the mixture to prevent coking- the deposition

and accumulation of carbon materials which leads to a decrease in the efficiency.

➢ Before being fed into the reactor, the streams of raw toluene and hydrogen are heated and

mixed with recycled toluene and hydrogen. Together with the undesired diphenyl, the

reactor's product stream also includes hydrogen, methane, benzene, and toluene. By

flashing away the light gases, we try to extract the majority of the hydrogen and methane

from the aromatics.

➢ Although methane, which is created during the reaction and enters the hydrogen stream as

an impurity, will build up in the gas-recycle loop, we would still prefer to recycle the

hydrogen that is left in the flash vapour. Therefore, in order to eliminate methane from the

process and product stream, a purge stream is needed.

We extract the majority of the leftover hydrogen and methane in a distillation column, known

as the stabiliser, to keep them from contaminating our benzene product because not all of it can

be separated from the aromatics in the flash drum. After recovering the benzene in a second

distillation column, the undesired diphenyl is eventually removed from the recycled toluene.

4
 Fig 1: HDA process flowsheet

3. STREAM TABLE DEVELOPMENT

It is known that the hydrodealkylation process happens when fresh toluene (pure) and a mixture
of 95% hydrogen and 5% methane are mixed with recycled toluene and hydrogen. We know
that the production rate of benzene in our process is 265 mol/hr. We aim to do the necessary
material and component balances and develop the stream table for the entire process.

We can also calculate the extent and selectivity of the reaction using our data to fabricate our
process output analysis accordingly.

Reaction: -
Toluene + H2 → Benzene + CH4
2 Benzene ↔ Diphenyl + H2

Given,

5
Production rate of Benzene, PB = 265 mol/hr
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐵𝑒𝑛𝑧𝑒𝑛𝑒 𝑝𝑟𝑜𝑑𝑢𝑐𝑒𝑑 0.0036
Selectivity (s) = = 1 – (1−𝑥)1.544 = 0.97 (when x = 0.75)
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑇𝑜𝑙𝑢𝑒𝑛𝑒 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑

𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑇𝑜𝑙𝑢𝑒𝑛𝑒 𝑟𝑒𝑎𝑐𝑡𝑒𝑑

Conversion (x) = = 0.75
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑇𝑜𝑙𝑢𝑒𝑛𝑒 𝑓𝑒𝑑

stream
Purge
Gas Feed Benzene

System
Toluene Diphenyl

Fig 2: Overall HDA schematic process flow sheet

We know that,

𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐵𝑒𝑛𝑧𝑒𝑛𝑒 𝑝𝑟𝑜𝑑𝑢𝑐𝑒𝑑

Selectivity =
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑇𝑜𝑙𝑢𝑒𝑛𝑒 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑

𝑃𝐵
FFT =
𝑠

We are assuming that no accumulation of hydrogen will occur in the system.

Input – Output + Generation – Consumption = 0

YFH FG – FE + PD - FFT = 0

(1−𝑠)
PD = PB
2𝑠

By, solving the above two equations, we get the following:

(𝟏+𝒔)
FE = YFH FG - PB
𝟐𝒔
(3)

where,

FE = excess H2 coming from Purge Stream

Similarly, by Balancing CH4 we get,

Input – Output + Generation – Consumption = 0

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 𝑃𝐵
FG (1-YFH) – FCH4 + =0
𝑠

𝑃𝐵
FCH4 = FG (1-YFH) + (4)
𝑠

By analysing the purge stream, we get the following:

PG = FE + FCH4

By (3) & (4),

(1+𝑠) 𝑃𝐵
PG = YFH FG - PB + FG (1-YFH) +
2𝑠 𝑠

(𝟏−𝒔)
PG = FG + PB (5)
𝟐𝒔
𝐹𝐸
YPH = (where YPH = mole fraction of hydrogen in purge stream)
𝑃𝐺

𝐹𝐸
PG =
𝑌𝑃𝐻

𝑌 (1+𝑠) 𝑃𝐺
Or PG = FG 𝑌𝐹𝐻 -
𝑃𝐻 2𝑠 𝑌𝑃𝐻

Rearranging it, we get:

𝑃𝐵 (𝑌𝑃𝐻 (𝑠−1)−(𝑠+1))
FG =
2𝑠 (𝑌𝑃𝐻 −𝑌𝐹𝐻 )

𝑷𝑩 (𝒀𝑷𝑯 (𝒔−𝟏)−(𝒔+𝟏)) (𝟏−𝒔)

PG = + PB
𝟐𝒔 (𝒀𝑷𝑯 −𝒀𝑭𝑯 ) 𝟐𝒔

(7) RG (5) PG

(8) PG + RG
(10) FR
(1) FG (4) PB
(9) PB + PD + RT + PG + RG
Reactor Separator

(2) FFT (3) PD

(11) FT

(6) RT
Fig 3: Detailed HDA Process flow sheet.
Let the inlet stream to the reactor for gas and Toluene feed be FRG and FT respectively,
We know that,
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 YRG FRG = M.R. FT (i.e. H2 / aromatic = M.R. = 5) (6)
𝐹𝑇 −𝑅𝑇
Also, x = 𝐹𝑇

RT = FT (1-x)
Now, by balancing Hydrogen at the inlet gas stream
YFH FG + YPH RG = M.R. FT
Substituting values of FG, FT we get:

𝑀.𝑅. 𝑃𝐵 𝑌𝐹𝐻 𝑃𝐵 (𝑌𝑃𝐻 (𝑠−1)−(𝑠+1))

RG = -
𝑌𝑃𝐻 𝑠 𝑥 𝑌𝑃𝐻 2𝑠 (𝑌𝑃𝐻 −𝑌𝐹𝐻 )

Also,

FR = FG + RG (7)

Substituting values of FG and RG, we get:

𝑃𝐵
FR = (M.R. + YPH (s-1) – (s+1))
2𝑠𝑌𝑃𝐻

Now, as known to us,

PB = 265 mol/hr

s = 0.969

x = 0.75

YPH = 0.4

YFH = 0.95

M.R. = 5

After substituting these values in results obtained, we get:

FFT = 274 mol/hr

PD = 4.2 mol/hr

FG = 497 mol/hr

RG = 3377 mol/hr

FT = 365 mol/hr

8
 FR = 3874 mol/hr

RT = 91 mol/hr

PG = 501 mol/hr

YRH = 0.47

Stream Table:

Stream nBenzene nToluene nDiphenyl nHydrogen nMethane

S1 - - - 472.15 24.85
S2 - 274 - - -
S3 - - 4.2 - -
S4 265 - - - -
S5 - - 200.4 300.6
S6 - 91 - - -
S7 - - - 1350.8 2026.2
S8 - - - 1551.2 2326.8
S9 265 91 4.2 1551.2 2326.8
S10 - - - 1820.78 2053.22
S11 - 365 - - -
Table 1: Stream table of the overall system

4. REACTOR DESIGN AND THERMODYNAMICS

Our next task focuses on the reactor design based on thermodynamic studies. Using the heat of
reaction values, we can estimate the required reactor heat load. Given individual components'
Cp and stream value flow rates, we have to design the reactor accordingly. The output can also
help us understand whether we operate the reactor isothermally or adiabatically. We also
analyse a case where we purge all the methane out of the process and recycle the hydrogen wit
100% efficiency to study the process behaviour accordingly. To constraint the system, we use
the temperature constraints of quenching the reactor effluent to 1150 ◦F to prevent coking and
the reactor outlet temperature < 1300 ◦F to prevent hydrocracking. With this information, we
can calculate the theoretical horsepower (hp) to compress the gas-recycle stream for a
centrifugal gas compressor and calculate the temperature of the gas stream at the compressor
outlet. The following data will help us in the physical design of the reactor, involving area
calculation for economic, fabrication and design purposes.
T = 1200℉ and P = 500 psia

Reactor heat load = Heat of the reaction x Fresh feed rate

For the HDA process, Toluene gets converted to benzene.

X = 0.75, Pb = 265 mol/hr, FFT = Pb/5 = 273 mol/hr, PD = 4.2 mol/hr

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Here, we can neglect heat of 2nd reaction thus,

QR = ∆𝐇R x FFT = (-21530) x (273)

= -5.878 x 106 Btu/hr

TR,in = 1150 ℉

From the table,

Cp for H2 = 7 Btu/mol ℉

Cp for CH4 = 10.1 Btu/mol ℉

Cp for Toluene = 48.7 Btu/mol ℉

We know that,

QR = F x Cp x (TR,in – TR,out)

If TR,out < 0 ℉, we any have to supply heat, mainly it is isothermal and not adiabatic.

If TR,out > 0 ℉, we don’t have to supply external heat → adiabatic.

o Toluene → F (Feed + Recycle) = F (274 + 91) = 365 mol/hr

o CH4 → F (FG) = 497 mol/hr
o H2 → F (Recycle) = 3377 mol/hr
➢ Cp (makeup gas) = 0.95 x 7 + 0.05 x 10.1 = 7.16 Btu/mol ℉
➢ Cp (recycle) = 0.4 x 7 + 0.6 x 10.1 = 8.86 Btu/mol ℉

QR = -5.878 x 106 = [365 x 48.7 + 497 x 7.16 + 8.86 x 3377] {Tin - Tout}

=> - 5.878 x 106 = 51254.24 {Tin - Tout}

=> -114.68 = {1150 - Tout} => TR,out = 1264.683 ℉

TR,out < 1300 ℉ → Constrained T

TR,out > 0 ℉ → No external heat required => Adiabatic process

If we purge unwanted CH4 directly with 100% efficiency and only recycle H2,

o No accumulation of unwanted CH4, thus reaction efficiency will improve.

o It will save a lot of H2 (Feed of H2 can be saved) as H2 is 100% recycled.
o Setting up such a separator may be really expensive; thus, costs will increase.

10
For the reactor design, we know that,

hA(∆T) = |QR|, where h is the overall heat transfer coefficient

h = 20 Btu/hr ft2 ℉

∆T = (1264.68 – 1150) ℉ = 114.68 ℉

QR = -5.878 x 106

A = (5.878 x 106)/(114.68 x 20) = 2562.78 ft2, is the area of the reactor.

The design equation for the theoretical horsepower (hp) for a centrifugal gas compressor is:

hp = [(3.03 x 10-5)/𝛾] . Pin . Qin .[(𝑃𝑜𝑢𝑡 /𝑃𝑖𝑛 )𝛾 - 1] (8)

𝛾 = 0.254

Pin = 1 atm = 14.7 psia

Pout = 500 psia

Qin = 3878 m3 /hr

∴ hp = [(3.03 x 10-5)/0.254].(147).(3878).[(500/14.7)0.254 -1] = 9.855 hp

We know that,

𝑇𝑜𝑢𝑡 𝑃
= ( 𝑃𝑜𝑢𝑡)𝛾 (9)
𝑇𝑖𝑛 𝑖𝑛

Tin = 100 ℉ and Tout = 244.92 ℉

5. FLASH COLUMN COMPONENT ANALYSIS

The flash column pressure (Pin = 465 psia, Pout = 550 psia) and the flash column temperature
is 100◦F. Our previous data can help calculate the composition of all the components left from
the flash column in both phases, using required calculations on Excel Solver based on the Rice-
Rachford equation.

Flash equations can be written:

1. Overall: F = V + L (10)
2. Component Balance: 𝐹𝑧𝑖 = 𝑉𝑦𝑖 + 𝐿𝑥𝑖 (11)
𝐹 𝐹
3. Using equation 5 and 6, we get: 𝑦𝑖 = (𝑉) 𝑧𝑖 + (1 − 𝑉) 𝑥𝑖 (12)

11
 𝑉 𝑦 𝑍𝑖 1
4. Substituting 𝜓 = 𝐹 and 𝐾𝑖 = 𝑥𝑖, we get: 𝐾𝑖 𝑥𝑖 = 𝜓
+(1 − 𝜓) 𝑥𝑖
𝑖

𝑧𝑖 𝑖 𝑧 ×𝐾
𝑖
5. Finally, we get: 𝑥𝑖 = 1+𝜓(𝐾𝑖 −1)
and 𝑦𝑖 = 1+𝜓(𝐾 −1)𝑖

Procedure:

1. 𝐹𝑧𝑖 = 𝑉𝑦𝑖 + 𝐿𝑥𝑖 implies 𝑓𝑖 = 𝑣𝑖 + 𝑙𝑖 , where 𝑓𝑖 = 𝑓𝑧𝑖 , 𝑉𝑖 = 𝑉𝑦𝑖 𝑎𝑛𝑑 𝐿𝑖 = 𝐿𝑥𝑖 .

2. Also, 𝑉 = Σ𝑓𝑖 and 𝐿 = Σ𝑓𝐽 .

Calculation:

For our calculations, we have used Newton-Raphson Method to solve the Rachford-Rice
Equation.

Species Ki Zi Values [(Moles)i/Total moles]

Toluene 0.00363 0.021471
Hydrogen 99.07 0.366004
Methane 20 0.549007
Benzene 0.0104 0.062527
Diphenyl 0.00008 0.000991

𝑉
𝜑= (𝐺𝑖𝑣𝑒𝑛 𝑖𝑛 𝑡ℎ𝑒 𝑝𝑟𝑜𝑏𝑙𝑒𝑚)
𝐹

𝜑 = 0.9198325 (as determined by Newton-Raphson method)

Stream table:

1) Vapor Stream

Component fi ki Vi Li
H2 1551.2 99.07 1549.8345 1.3634
CH4 2326.8 20.00 2316.7055 10.0956
Table 2a: Stream table of vapor phase.

2) Liquid Stream

Component fj kj Vj Lj
Benzene 265 0.0140 28.2511 236.7513
Toluene 91 0.00363 3.6386 87.3599
Diphenyl 4.2 0.00008 0.00385 4.1962

12
 Table 2b: Stream table of liquid phase.

6. HEAT EXCHANGER DESIGN

Assuming we can recover 75% of heat from an exchanger, taking reactor flux and effluent
values, we can calculate the area of the heat exchanger which will aid us in the design and
manufacturing process of the same.

1. We fix a counter current heat exchanger after the reactor for maximum efficiency.

Assumptions:

• Th,in = 1264.68 F
• Tc,in = 77 F (Ambient Temperature, room temperature)
• ε = 0.75 (75% exchange)
• h (effluent) = h (influx) = 0.69 kW/m2K (as we ignored the difference between inner
and outer area)
Calculations:

• Overall Heat Transfer Coefficient U:

1 1 1
= +
𝑈 ℎ𝑒𝑓𝑓 ℎ𝑖𝑛𝑓
• Putting values of h, we get U = 0.345 kW/m2K- RESULT 1
• =345 W//m2K

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 • =60.76 Btu/hr ft2 F

At 1264.6 F = 957.5 K, efflux contains benzene, diphenyl, toluene, hydrogen and

methane. We calculated specific heats of components at 957.5 K using NIST values:
a) Cp (Benzene) = 50.4093 BTU/ lb mol F
b) Cp (Diphenyl) = 99.6779 BTU/ lb mol F
c) Cp (Toluene) = 62.6 BTU/ lb mol F
d) Cp (Hydrogen) = 7.187 BTU/ lb mol F
e) Cp (Methane) = 17.016 BTU/ lb mol F
Taking the weighted average of specific heat by multiplying it with flow rates from
the stream table S9 in the below table,

Stream nBenzene nToluene nDiphenyl nHydrogen nMethane

S1 - - - 472.15 24.85
S2 - 274 - - -
S3 - - 4.2 - -
S4 265 - - - -
S5 - - 200.4 300.6
S6 - 91 - - -
S7 - - - 1350.8 2026.2
S8 - - - 1551.2 2326.8
S9 265 91 4.2 1551.2 2326.8
S10 - - - 1820.78 2053.22
S11 - 365 - - -

We get Ch= 70,217.75 BTU/ lb mol F

Similarly, for the feed of reactor (toluene, hydrogen and methane) entering at ambient
temperature = 298.15 K,
a) Cp (Toluene) = 34.597 BTU/ lb mol F
b) Cp (Hydrogen) = 6.87 BTU/ lb mol F
c) Cp (Methane) = 8.55 BTU/ lb mol F
Taking the weighted average of specific heat by multiplying it with flow rates we get:
We get Cc= 12,935.72 BTU/ lb mol F
C = Cc/ Ch = 0.184
When Cc is Cmin
𝑇𝑐,𝑜𝑢𝑡−𝑇𝑐,𝑖𝑛
ε = 0.75 = 𝑇ℎ,𝑖𝑛−𝑇𝑐,𝑖𝑛

Putting values of known temperatures, we get Tc,out = 967.757 F,

For Th,out:

14
 ∆𝑄(ℎ𝑜𝑡) = ∆𝑄(𝑐𝑜𝑙𝑑) + ∆𝑄(𝑣𝑎𝑝𝑜𝑢𝑟𝑖𝑠𝑎𝑡𝑖𝑜𝑛)
Where ∆𝑄(𝑣𝑎𝑝𝑜𝑢𝑟𝑖𝑠𝑎𝑡𝑖𝑜𝑛) = 𝑚𝐿
On solving we get Th, out = 1044.39 F
Now, NTU = UAS/ Cmin
For counter-flow heat exchanger,
1 ε−1
NTU = 𝑐−1 ln εc−1

Substituting values, we get NTU = 1.52 = UAS/ Cmin

Thus AS = 322.92 ft2= 30.0 m2 - RESULT 3
Using D=5 cm, we get l of pipe = 191.1 m
Total heat exchanged= Heat lost by hot fluid
Q = Ch (Th,in – Th,out)
Q =1.54 × 𝟏𝟎𝟕 BTU/hr is the heat exchange rate. – RESULT 4

7. MULTICOMPONENT DISTILLATION COLUMN USING FUG &

KIRKBRIDE METHOD
We next focus on separating the components after the reaction through multicomponent
distillation. In distillation, the light key (LK) is the more volatile component that primarily goes
to the distillate, while the heavy key (HK) is the less volatile component that remains in the
bottom stream. In this case, benzene is the light key, as it is recovered at 99.5% in the top
stream, while toluene is the heavy key, with 98% recovery in the bottom stream, along with
diphenyl, the heaviest component. We can solve the same using FUG and Kirkbride methods
to extract required data about components and stream flow rates, number of stages, feed
location, reflux ratio, minimum number of stages and minimum reflux ratio required to carry
the process efficiently.

Excel solver link: Group 3_APE_Sheet.xlsx

Given :- 99.5% recovery of Benzene (light key) in the top stream

➢ Mole Fraction of Benzene in top stream (Distillate) = 0.995

➢ Remaining 0.005 Mole Fraction is of Toluene & Diphenyl combined

98% recovery of Toluene (Heavy key) at the bottom stream along with Diphenyl

➢ Mole Fraction of Toluene & Diphenyl combined in bottom stream = 0.98

➢ Remaining 0.2 Mole Fraction is of Benzene in Bottom

Stream Table:

15
Now, for calculation of Bottom & Distillate moles, we will do material balance of Benzene in
multicomponent distillation column.

Material balance for Benzene:

1. Overall : F = B + D
➢ 360.2 = B + D ….(13)

2. Component : 𝐹𝑥𝑓 = 𝐵𝑥𝑏 + 𝐷𝑥𝑑

➢ 360.2 × 0.7357 = B × 0.2 + D × 0.995 ….(14)

3. From equation (13) & (14), we get B = 95.7923 mol/hr & D = 264.4081 mol/hr.

As given in the problem,

➢ Benzene = Light Key (LK)

➢ Toluene = Heavy Key (HK)
➢ Diphenyl = Heavy Non-Key (NK)

Minimum Number of Stages

Fenske Equation to give an estimate of the min. number of stages:
𝑥𝐿𝐾 𝑥
log [( ) ( 𝐻𝐾 ) ]
𝑥𝐻𝐾 𝑑 𝑥𝐿𝐾 𝑏
𝑁𝑚 =
log 𝛼𝐿𝐾−𝐻𝐾
𝐾 0.0104
Where, 𝛼LK-HK = 𝐾 𝐿𝐾 = 0.00363 = 2.865
𝐻𝐾

Here, HK is of both Toluene & Diphenyl for calculating Nmin

0.995 0.98
log[(0.005)(0.02)]
Nmin = 0.0104 => 𝑁𝑚𝑖𝑛 = 8.7264
log[0.00363]

The mole fraction of Toluene along with Diphenyl in the distillate & in the bottom is 0.005,
0.98 respectively.
Let the mole fraction of Diphenyl in the distillate be x & in the bottom, be y.
Mole fraction of Toluene in distillate will be 0.005 – x & in bottom be 0.98 – y.

16
Material balance for Diphenyl :
Component balance :- 𝐹𝑥𝑓 = 𝐵𝑥𝑏 + 𝐷𝑥𝑑

➢ 360.2 × 0.01166 = 95.7923 × y + 264.4081 × x

4.200056−95.7923𝑦
➢ 𝑥= ....(15)
264.4081

Using Fenske Equation to calculate x & y,

For NK-HK,
𝑥 𝑥 𝑥 0.98 − 𝑦
log [(𝑥𝑁𝐾 ) (𝑥𝐻𝐾 ) ] log [( ) ( ) ]
𝐻𝐾 𝑑 𝑁𝐾 𝑏 0.005 − 𝑥 𝑑 𝑦 𝑏
𝑁𝑚 = =
log 𝛼𝑁𝐾−𝐻𝐾 0.00008
log (0.00363)

𝑥 0.98 − 𝑦
log [( ) ( ) ]
0.005 − 𝑥 𝑑 𝑦 𝑏
=> 8.7264 =
log(0.02204)
Putting the value of x from equation (15) in above, we got the value of x and y as:
=> 𝑦 = 0.04384 𝑎𝑛𝑑 𝑥 = 1.97258 × 10−6

Feed composition Distillate composition Bottom composition

Molar Flow Mole Molar Flow Mole Fraction Molar Mole
Species Rate Fraction (xf) Rate (xd) Flow Rate Fraction (xb)
Benzene
(LK) 265.0019314 0.735706974 263.0860595 0.995 1.915846 0.02
Toluene
(HK) 90.9983922 0.252632694 1.32161 0.0049984 89.67678 0.93616
Diphenyl
(NK) 4.2000562 0.011660333 0.000522 1.97258 ×10-6 4.199534 0.04384

Total 360.2003798 264.4081 95.7923

Now, we know exact composition of mole fraction of toluene in distillate and bottom,
Therefore, a more accurate estimate of Nmin can be obtained by putting these values.
𝑥 𝑥
log [(𝑥 𝐿𝐾 ) ( 𝑥𝐻𝐾 ) ]
𝐻𝐾 𝑑 𝐿𝐾 𝑏
𝑁𝑚 =
log 𝛼𝐿𝐾−𝐻𝐾

17
 0.995 0.93616
log [(0.004998) ( 0.02 )]
=> => 𝑵𝒎𝒊𝒏 = 𝟖. 𝟔𝟖𝟑𝟐
0.0104
log [0.00363]

Minimum Reflux Ratio

Species Ki 𝛼i xi,f 𝛼ixi,f xi,d 𝛼ixi,d

Benzene
(LK) 0.0104 2.865013774 0.735706974 2.107810614 0.995 2.850688705

Toluene
(HK) 0.00363 1 0.252632694 0.252632694 0.0049984 0.0049984

Diphenyl
(NK) 0.00008 0.022038567 0.011660333 0.000256977 1.97258×10-6 4.34728E-08

Here, 𝜶𝒊 signifies average relative volatility of the component i with respect to the reference
component (Heavy Key) :
𝐾𝑖
𝛼𝑖 = 𝑤ℎ𝑒𝑟𝑒 𝐾𝑟𝑒𝑓𝑒𝑟𝑒𝑛𝑐𝑒 𝑖𝑠 𝑡𝑎𝑘𝑒𝑛 𝑎𝑠 𝐾 𝑜𝑓 𝑇𝑜𝑙𝑢𝑒𝑛𝑒
𝐾𝑟𝑒𝑓𝑒𝑟𝑒𝑛𝑐𝑒
𝐾𝐵𝑒𝑛𝑧𝑒𝑛𝑒 0.0104
• 𝛼𝐵𝑒𝑛𝑧𝑒𝑛𝑒 = = = 2.865
𝐾𝑇𝑜𝑙𝑢𝑒𝑛𝑒 0.00363
𝐾𝑇𝑜𝑙𝑢𝑒𝑛𝑒 0.00363
• 𝛼 𝑇𝑜𝑙𝑢𝑒𝑛𝑒 = = =1
𝐾𝑇𝑜𝑙𝑢𝑒𝑛𝑒 0.00363
𝐾𝐷𝑖𝑝ℎ𝑒𝑛𝑦𝑙 0.00008
• 𝛼𝐷𝑖𝑝ℎ𝑒𝑛𝑦𝑙 = = = 0.022
𝐾𝑇𝑜𝑙𝑢𝑒𝑛𝑒 0.00363

It is given that we have a saturated liquid, so for that, the q value will equal to 1.
Using the Underwood Equation to estimate the minimum reflux ratio,
𝛼𝑖 × 𝑥𝑖,𝑓
∑ = 1−𝑞
𝛼𝑖 − 𝜃
Where, θ is the root of the equation.
Expanding the above equation, we get:
𝛼𝐵𝑒𝑛𝑧𝑒𝑛𝑒 × 𝑥𝑓,𝐵𝑒𝑛𝑧𝑒𝑛𝑒 𝛼 𝑇𝑜𝑙𝑢𝑒𝑛𝑒 × 𝑥𝑓,𝑇𝑜𝑙𝑢𝑒𝑛𝑒 𝛼𝐷𝑖𝑝ℎ𝑒𝑛𝑦𝑙 × 𝑥𝑓,𝐷𝑖𝑝ℎ𝑒𝑛𝑦𝑙
+ + =1−𝑞
𝛼𝐵𝑒𝑛𝑧𝑒𝑛𝑒 − 𝜃 𝛼 𝑇𝑜𝑙𝑢𝑒𝑛𝑒 − 𝜃 𝛼𝐷𝑖𝑝ℎ𝑒𝑛𝑦𝑙 − 𝜃
2.017811 0.25263 0.000257
=> + + = 0 => 𝜃 = 1.19964
2.865014 − 𝜃 1−𝜃 0.02204 − 𝜃
Now,
𝛼𝑖 × 𝑥𝑖,𝑑
∑ = 𝑅𝑚 + 1
𝛼𝑖 − 𝜃
Expanding the above equation, we get:

18
 𝛼𝐵𝑒𝑛𝑧𝑒𝑛𝑒 × 𝑥𝑑,𝐵𝑒𝑛𝑧𝑒𝑛𝑒 𝛼 𝑇𝑜𝑙𝑢𝑒𝑛𝑒 × 𝑥𝑑,𝑇𝑜𝑙𝑢𝑒𝑛𝑒 𝛼𝐷𝑖𝑝ℎ𝑒𝑛𝑦𝑙 × 𝑥𝑑,𝐷𝑖𝑝ℎ𝑒𝑛𝑦𝑙
+ + = 𝑅𝑚 + 1
𝛼𝐵𝑒𝑛𝑧𝑒𝑛𝑒 − 𝜃 𝛼 𝑇𝑜𝑙𝑢𝑒𝑛𝑒 − 𝜃 𝛼𝐷𝑖𝑝ℎ𝑒𝑛𝑦𝑙 − 𝜃

2.850688705 0.0049984 4.34728 ∗ 10−8

=> + + = 𝑅𝑚 + 1
2.865013774 − 1.19964 1 − 1.19964 0.02204 − 1.19964
On solving the above, we get Rm = 0.6867

Actual Number of Stages

The recommended value of R/Rmin to use with the Gilliland method is typically in the range of
1.1 to 1.5, with the lower value for difficult separations requiring more than 100 equilibrium
stages and the higher value for easy separations of less than 10 equilibrium stages. Since we
have the Nm equal to 8.6832, which means the equilibrium stages are less than 10. Thus, we
are considering the R/Rmin ratio as 1.5 which gives the R value as 1.030056 (approx.)

𝑅− 𝑅𝑚𝑖𝑛
Let’s consider = 𝑋.
𝑅+1
1.030056−0.6867
 𝑋 = = 0.169134248
2.030056

Now,
Gilliland Correlation for graph is given as below:
1
𝑌 = 0.2788 − 1.3154𝑋 + 0.4114𝑋 0.2910 + 0.8268 ln 𝑋 + 0.9020 ln (𝑋 + )
𝑋
𝑁− 𝑁𝑚𝑖𝑛 𝑅− 𝑅𝑚𝑖𝑛
where, Y = and X =
𝑁+1 𝑅+1

On putting the X value in above equation, we got Y = 0.460686607

𝑁− 𝑁𝑚𝑖𝑛
 = 0.460686607
𝑁+1
 𝑁 = 16.95468112
Thus, actual number of stages equals to 16.95468112 ≈ 𝟏𝟕.

Feed Location
Total Number of Stages = 16.95468112 = NR + NS ….(16)
The empirical equation given by Kirkbride is:

19
Where, NR = number of stages above the feed, including any partial condenser.
NS = number of stages below the feed, including the reboiler.
2 0.206
𝑁𝑅 0.25263269 0.02 95.7923
=> = [(0.735706974) (0.0049984) (264.4081)] = 1.15250583
𝑁𝑆

=> 𝑁𝑅 = 1.15250583 × 𝑁𝑆 ….(17)

From equations (16) & (17),
NS = 7.876717862 ≈ 8
NR = 9.077963262 ≈ 9
So, feed will enter at 9th plate which is calculated from top of the column.

Composition of Top and Bottom Stream

Feed composition Distillate (Top) composition Bottom composition

Molar Flow Mole Molar Flow Mole Fraction Molar Mole
Species Rate Fraction (xf) Rate (xd) Flow Rate Fraction (xb)
Benzene
(LK) 265.0019314 0.735706974 263.0860595 0.995 1.915846 0.02
Toluene
(HK) 90.9983922 0.252632694 1.32161 0.0049984 89.67678 0.93616
Diphenyl
(NK) 4.2000562 0.011660333 0.000522 1.97258 ×10-6 4.199534 0.04384

Total 360.2003798 264.4081 95.7923

8. McCABE-THIELE METHOD:
Since benzene has already been separated in the first column, the second column will
separate the remaining mixture of toluene and diphenyl. Here, toluene is the light key as it
is recovered at 99.5% in the top stream for recycling, while diphenyl is the heavy key
with a 99% recovery in the bottom stream. The McCabe–Thiele method will be used to
design this separation.
• Objective: To achieve 99.5% recovery of toluene in the distillate and 99% recovery
of diphenyl in the bottom product.
• Input Data:
o Feed composition (Excel Solver-derived):
▪ Toluene in feed: 89.58 mol/hr
▪ Diphenyl in feed: 4.20 mol/hr
Step-by-Step Calculation
20
 8.1 Distillate and Bottom Composition
• Moles of Toluene:
o Distillate: 0.995×89.58=89.23 mol/hr
o Bottom: 89.58−89.23=0.042 mol/hr
• Moles of Diphenyl:
• Distillate: 0.45 mol/hr
• Bottom: 4.20−0.45=4.1258 mol/hr
• Compositions:
Moles of Toluene in Distillate
• Distillate(xD)= = 0.999
Total moles in Distillate
Moles of Toluene in Bottom
• Bottom(xB ) = = 0.097
Total moles in Bottom
Moles of Toluene in Feed
• Feed(xF ) = = 0.9552
Total moles in Feed

x’= xF = 0.9552 (since, q=1, therefore, x’=xF)

8.2 Minimum Reflux Ratio (Rmin):
𝑅𝑚 𝑥𝐷 − 𝑦′
=
𝑅𝑚 + 1 𝑥𝐷 − 𝑥′
Where:
• y′: Enrichment line intersection value
• xD: Distillate composition
• x′: Feed composition

On solving we get,
Rmin= 2.129

8.3 Operating Reflux Ratio (RRR)

𝑅
Since, = 1.2
𝑅𝑚𝑖𝑛

Hence, Reflux ratio= 2.768

8.4 Stages:

Through McCabe Thiele graphical method, we get, N=9-1=8 ideal stages + 1 Reboiler
N=8 stages

𝑁
𝑁𝑚𝑖𝑛 = = 4 𝑠𝑡𝑎𝑔𝑒𝑠 𝑚𝑖𝑛𝑖𝑚𝑢𝑚
2
Also, feed location is at plate 1

21
 8.5 Rectifying line equation:
𝑅𝐷 𝑋𝐷
𝑦𝑛+1 = 𝑋𝐷 +
𝑅𝐷 + 1 𝑅𝐷 + 1
y = 0.7346x+ 0.2652 (used in graphical method)

9. CONCLUSION
This report presents a detailed analysis of the Hydrodealkylation of Toluene (HDA) process
for benzene production. The study incorporates material and energy balance, process
optimization, and design considerations. Key achievements include:

• Material Balance: Comprehensive calculations of feed, product, and recycle streams

were conducted, resulting in accurate stream compositions.
• Energy Analysis: Reactor heat loads and heat exchanger designs were evaluated,
ensuring efficient energy usage and minimized losses.

22
 • Distillation Column Design: Using Fenske, Underwood, and Gilliland methods, the
distillation process was optimized to achieve high recovery rates of benzene and
efficient separation of byproducts.
• McCabe-Thiele Method: Equilibrium stages and feed locations were accurately
determined, verifying the operational parameters of the distillation process.
• Process Efficiency: The necessity of quenching, recycle streams, and purge systems to
prevent coking and manage impurities like methane was established, ensuring smooth
and efficient process operation.

Overall, the report successfully demonstrates the HDA process's theoretical and practical
aspects, aligning with the principles of applied process engineering. These findings
contribute to understanding and optimizing the industrial-scale production of benzene.

10. REFERENCES AND CITATIONS

➢ De Araújo, A. C. B., Govatsmark, M. S., & Skogestad, S. (2007). Application of

plantwide control to the HDA process. I—steady-state optimization and self-optimizing
control. Control Engineering Practice, 15(10), 1222–1237.
https://doi.org/10.1016/j.conengprac.2006.10.014
➢ R. H. Perry, “Perry’s Chemical Engineers’ Handbook,” 9th Edition, McGraw-Hill, New
York, 2018.

➢ Rachford, H. H. Jr, and J. D. Rice. “Procedure for Use of Electronic Digital Computers
in Calculating Flash Vaporization Hydrocarbon Equilibrium.” Journal of Petroleum
Technology 4, no. 10 (October 1, 1952): 19-3. doi:10.2118/952327-G.

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1. APPENDIX

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APE 3: Assignment 2 Question 4:

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APE 3: Final Assignment

42
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Final Assignment Part 2: McCabe Thiele Graphical Method:

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