CDB 3044

PROCESS PLANT DESIGN

JANUARY 2018 SEMESTER

MINI PROJECT
HYDRODEALKYLATION PROCESS

GROUP MEMBERS : 1. Ahmad Aliyan Alif bin Ismail (24121)

2. Velisia Chandra Gunawan (24084)
LECTURER : KHOR CHENG SEONG
SUBMISSION DATE : FRIDAY 13 APRIL 2018
 INTRODUCTION

In this mini project, hydrodealkylation (HDA) process of toluene to produce benzene (main reaction) is
studied. The process includes reversible process of benzene and diphenyl as side reaction. Hydrogen is supplied in
excess along with Toluene as main raw material. Impurities exist by Methane in Hydrogen stream (5%). No catalyst
involved with intention to produce 265 kmol/h of benzene in range of 620-740 C with pressure drop range 2-4 bara.
Purge gases are produced along with recycle process to achieve desired product flowrate. By-product diphenyl is to
be recovered and removed. All the flowrates are calculated by stating some assumptions on material balance regarding
conversion and purge composition. Specifically, the values chosen for the process are 60% conversion and 40%
purge gas composition. Other information can be found at Appendix. Some factors analyzed: small production
volume < 500 ton/year; multiproduct obtained and operational issues, gives decision to be operated as batch.

Details on input and output structure of HDA process such as feed purification, recovering or recycling by
products and reactants, purging gas, and number of streams taken into considerations. In feed purification, toluene
which methane gas exists in small quantity, a decision to purify or to proceed and separate later is chosen. Recycling
is considered in the process to lessen the expensive raw material cost and increase the yield of byproducts. Two
different phases lead to two types of recycling: liquid and gas. Propene with boiling point of -48°C is taken as limit to
separate the two recycles. Higher than the point (H2, CH4) will be taken into gas recycle. Lower boiling points
(Benzene, Toluene and Diphenyl) will be continued to liquid recycle. Streams needed in the process design are started
with fresh feed and products (main and byproduct) streams. Several other streams are waste, recycle, purge and fuel.
The best reason to have specific streams is to avoid mixing after separating two streams.

Level 1: INPUT INFORMATION AND BATCH VS CONTINUOUS

1. Reaction Information

Toluene + 𝑯𝟐  Benzene + 𝑪𝑯𝟒

2 Benzene ↔ Diphenyl + 𝑯𝟐
Inlet temperature  620C, reactor pressure = 34 bara
Gas phase
0.0036
Conversion and selectivity relationship: 𝑆 = 1 − ,𝑥 ≤ 0.97,
(1−𝑥)1.544
No catalyst
2. Production rate = 265 kmol/hr of benzene
3. Purity of benzene = 0.9997
4. Raw materials: Pure toluene at ambient conditions; H2 stream at 95% H2, 5% CH4 at 38C, 38 bara
5. Constraints: H2/aromatics  5 in reactor feed (prevent coking); Tout  704C (prevent hydrocracking); quick
quench after reactor to  620C (prevent coking)

1
LEVEL 2:INPUT-OUTPUT STRUCTURE

Toluene Hydrogen, Methane

Hydrogen, Methane
Diphenyl
HDA process
Toluene Benzene

Figure 2.1 Level 2 Flowsheet of HDA process

In this level, the gas to be purified is the recycled H 2 gas. This is done by purging methane to reduce the
impurities in the system. The Diphenyl by-product is assumed to be recovered and removed 100%. The purging on
light ends gas follows the boiling point, which is summarized in Table 1.

Table 2.1.: Boiling point of the reactant, product and by-product of the HDA process.

Components Boiling Point

H2 -253 oC
Gas Recycle
CH4 -161 oC
C3H6 -50 oC
Benzene 80 oC
Toluene 111 oC Liquid Recycle
Diphenyl 255 oC

In this level we assume the system is perfect separation. For toluene recovery, we assume it is 100% converted
and recycled on liquid recycle system, while the H2 gas is recycled 100% in vapor form, but some of the H 2 gas will
be lost in the purge stream alongside with methane. The calculation and derivation for Level 2 can be found in
Appendix while the Cost Data (Table 2) and Economic Potential Relation for EP2 can be summarized in Eq. (1)
below:

EP2 = Product Value + Byproduct Value – Raw Material Cost + Diphenyl Fuel Value+ Purge gas value (1)

Table 2.2: Cost Data

Components Flowrate (kmol/h) Cost (RM/kmol) Fuel Cost (RM/kmol)

Benzene 265 34.35
Toluene 273.365 24.32
Diphenyl 4.1824 20.45
Hydrogen (H2) 466.9825 4.32 1.87
Methane (CH4) 5.82

Work Hours per year = 8150 hour/year

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Finishing level 2, the values of EP2 can be calculated and presented in the Graph 2.1 below. The values are
negative for purge composition at 90%.

EP2 Values vs Conversion

yph0.1 yph0.4 yph0.7

26000000
24000000
22000000
20000000
RM/year

18000000
16000000
14000000
12000000
10000000
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.75 0.8 0.9
Conversion, x

Graph 2.1 EP Level 2 versus Conversion Values showing Positive Values from ypH 0.1, 0.4, 0.7.

In Graph 2.2, the EP level 2 decreases the more gas purged out from the process. For 0.7 and 0.9, the EP becomes
negative. Thus profits can be obtained at 0.1 and 0.4.

Energy Potential Level 2 for 60% Conversion

30000000
20000000
10000000
0
RM/year

-10000000
-20000000
-30000000
-40000000
-50000000
-60000000
-70000000
0.1 0.4 0.7 0.9
Mole fraction of Hydrogen at Purge Gas (yPH)

Graph 2.2 EP Level 2 shows decrement as increment of purge gas composition

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Level 3: Recycle Structure

Figure 3.1 Recycle Flowsheet

For HDA process, since the reaction only involve in a single stage, we only need one reactor in a continuous
process. There is no separation in the reactor system as there is only one reactor. Thus, the recycle stream needed is
only one (for gas) and one (for liquid). To prevent coking, we need to supply excess H2 by recycling the H2 gas. The
recycle material balance is developed in Appendix. Since we have to recycle H2, a gas compressor is required and the
cost for our gas compressor is estimated to be MYR 3,084,949 with y PH=0.4 and conversion x, = 0.6. In this case, we
assume that the reactor should be operated adiabatically with direct heating (to 620°C) and for this level, we assume
that steam is required to supply heat to the reactor. In this level, we recycle toluene to ensure the equilibrium
conversion to be small. The reactor cost and compressor cost relation to Economic Potential is expressed in eq. (2)
below and the EP3 relation to conversion, x is plotted in Graph 3.1.

EP3 = EP2 – Compressor Cost – Reactor Cost (2)

EP 3 vs Conversion, x
0.1 0.4 0.7

20,000,000.00
EP3 value (MYR/yr)

15,000,000.00

10,000,000.00

5,000,000.00

0.00
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Conversion,x

Graph 3.1: EP3 vs conversion

4
From Graph 3.1, the values for yPH= 0.7 and yPH = 0.9 is discarded as they present negative values for EP3. This
graph also concluded that for EP3, yPH= 0.4 has the highest EP value (MYR18 million) at conversion, x=0.6. Below
shown Graph 3.2 to present the profitable purge gas composition at 0.1 through 0.4 only.

Energy Potential Level 3 for 60% Conversion

40,000,000.00
20,000,000.00
0.00
-20,000,000.00
$/year

-40,000,000.00
-60,000,000.00
-80,000,000.00
-100,000,000.00
-120,000,000.00
0.1 0.4 0.7 0.9
Mole fraction of Hydrogen at Purge Gas (yPH)

Graph 3.2 EP3 at different purge gas composition

Level 4 SEPARATION SYSTEM STRUCTURE

This project has done theoretical design on level 4 of HDA process which can be found in Appendix.

CONCLUSION

Based on the EP values that has been calculated, at x=0.6 and yph=0.1 gives EP2 RM 24,173,721/year and
EP3 RM 13,600,781/year which is profitable and can be maximized by trying other conversion and purge composition.
The volume size of reactor is 10.4 m3 with a dimension of D=1.39 m, L=6.93m (L/D =5). Compressor cost is
RM4,490,690/year with allowable 4-6 bara maximum pressure drop.

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 APPENDICES

Level 1 INPUT OUTPUT INFORMATION

mol of Benzene formed
Selectivity 𝑠 =
mole of Toluene converted

mole of Toluene converted

Conversion 𝑥 =
mole of Toluene fed

Level 2 INPUT OUTPUT STRUCTURE

1. Single pass conversion

Assume no Toluene recycled.

Toluene unreacted
(1-x) mol
Toluene feed
(1 mol) Benzene formed
sx mol
Toluene reacted
x mol
Diphenyl formed
½ (s-sx) mol

Toluene + 𝐻2  Benzene + 𝐶𝐻4

x sx

2 Benzene ↔ Diphenyl + 𝐻2

sx ½ (x-sx)

𝑃𝐵 𝑃𝐵
𝑠= 𝐹𝐹𝑇 =
𝐹𝐹𝑇 𝑠

ypH = 0.1 and x = 0.6

0.0036
𝑆 =1− = 0.98518
(1−0.6)1.544

2. Byproducts Flowrate
1 1
𝑃𝐷 = (1 − 𝑠)𝑥 = (1 − 𝑠)𝐹𝐹𝑇
2 2
𝑃𝐻2 = 𝐹𝐸
𝐹𝐸 = 𝑦𝑃𝐻 𝑃𝐺

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3. Feed Flowrate

𝐹𝐻2 = 𝐹𝑅,𝐻2 + 𝐹𝐸

𝐹𝑅,𝐻2 = net H2 requirements (H2 reacted with Toluene – H2 formed with Diphenyl)
𝑃𝐵 1
𝐹𝑅,𝐻2 = [1 − (1 − 𝑠)]
𝑠 2

𝑃𝐶𝐻4 = 𝐹𝐶𝐻4 + 𝑃𝑅,𝐶𝐻4

𝐹𝐶𝐻4 = (1 − 𝑦𝐹𝐻 ) 𝐹𝐺
𝑃𝐵
𝑃𝑅,𝐶𝐻4 =
𝑠

𝐹𝐻2 = 𝐹𝑅,𝐻2 + 𝐹𝐸
𝑃𝐵 1
𝑦𝐹𝐻 𝐹𝐺 = [1 − (1 − 𝑠)] + 𝑦𝑃𝐻 𝑃𝐺
𝑠 2

𝐹𝐸 = 𝐹𝐻2 − 𝐹𝑅,𝐻2
𝑃𝐵 1
𝑦𝑃𝐻 𝑃𝐺 = 𝑦𝐹𝐻 𝐹𝐺 − [1 − (1 − 𝑠)] (a)
𝑠 2

𝑃𝐶𝐻4 = 𝐹𝐶𝐻4 + 𝑃𝑅,𝐶𝐻4

𝑃𝐵
(1 − 𝑦𝑃𝐻 ) 𝑃𝐺 = (1 − 𝑦𝐹𝐻 ) 𝐹𝐺 + (b)
𝑠

Adding (a) and (b),

𝑷𝑩 𝟏
𝑷𝑮 = 𝑭𝑮 + [ (𝟏 − 𝒔)]
𝒔 𝟐

Substitute this 𝑃𝐺 value into equation (a)

𝑃𝐵 1 𝑃𝐵 1
𝑦𝑃𝐻 𝐹𝐺 + [ (1 − 𝑠)] = 𝑦𝐹𝐻 𝐹𝐺 − [1 − (1 − 𝑠)]
𝑠 2 𝑠 2

𝑃𝐵 𝑃𝐵
(1 − 𝑠)(𝑦𝑃𝐻 − 1) = 𝐹𝐺 (𝑦𝐹𝐻 − 𝑦𝑃𝐻 ) −
2𝑠 𝑠

𝑃𝐵
(𝑦𝑃𝐻 − 1 − 𝑠𝑦𝑃𝐻 + 𝑠 + 2) = 𝐹𝐺 (𝑦𝐹𝐻 − 𝑦𝑃𝐻 )
𝑠
𝑷𝑩
𝑭𝑮 = (𝒚 − 𝒔𝒚𝑷𝑯 + 𝒔 + 𝟏)
𝟐𝒔 (𝒚𝑭𝑯 − 𝒚𝑷𝑯 ) 𝑷𝑯

EP2 = Product Value + Byproduct Value – Raw Material Cost + Diphenyl Fuel Value

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Level 3 RECYCLE STRUCTURE

Adiabatic Temperature Change

Component ∆𝐻𝑓 (𝑘𝐽/𝑘𝑚𝑜𝑙) 𝐶𝑝 (𝑘𝐽/𝑘𝑚𝑜𝑙. ℃)

Hydrogen 0 52,500
Methane -74,860 67,200
Toluene 50,030 150,700
Benzene 82,980 194,500
Diphenyl 182,210 374,700

By using the formula above, the Temperature in is assumed to be 620℃ with Temperature out obtained 620.095℃.
Thus, Adiabatic is applied. This only consider first or main reaction.

1. Material Balance for Excess Reactant

𝑚𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝐻2
𝑀𝑅 = ≥5
𝑚𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑇𝑜𝑙𝑢𝑒𝑛𝑒

𝑦𝐹𝐻 𝐹𝐺 + 𝑦𝑃𝐻 𝑅𝐺 = 𝐹𝐻

𝑦𝐹𝐻 𝐹𝐺 + 𝑦𝑃𝐻 𝑅𝐺 = 𝑀𝑅 𝐹𝑇
1 𝑃𝐵
𝑅𝐺 = [(𝑀𝑅 ) − 𝑦𝐹𝐻 𝐹𝐺 ]
𝑦𝑃𝐻 𝑠𝑥

𝟏 𝑷𝑩 𝑷𝑩
𝑹𝑮 = [(𝑴𝑹 ) − 𝒚𝑭𝑯 (𝒚𝑷𝑯 − 𝒔𝒚𝑷𝑯 + 𝒔 + 𝟏)]
𝒚𝑷𝑯 𝒔𝒙 𝟐𝒔 (𝒚𝑭𝑯 − 𝒚𝑷𝑯 )

where (𝑦𝑃𝐻 − 𝑠𝑦𝑃𝐻 + 𝑠 + 1) ≈ 1

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2. Compressor Cost Calculation (Douglas,1988)
3.03x105 𝑃𝑜𝑢𝑡 𝛾
Compressor power,(bhp) hp=( ) 𝑃𝑖𝑛 𝑄𝑖𝑛 [( ) − 1) x 𝑅𝐺
𝛾 𝑃𝑖𝑛

Where; 𝛾 = 0.236 (𝑓𝑜𝑟 𝐻𝐷𝐴 𝑝𝑟𝑜𝑐𝑒𝑠𝑠 𝑎𝑡 𝑝𝑢𝑟𝑔𝑒 𝑐𝑜𝑚𝑝𝑜𝑠𝑖𝑡𝑖𝑜𝑛 10%

ℎ𝑝 0.3853
Compressor cost, i) Operating compressor cost = x x 8150 hr/yr
𝜂 1.341

Where; 𝜂 = 𝑐𝑜𝑚𝑝𝑟𝑒𝑠𝑠𝑜𝑟 𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑐𝑦

𝑀&𝑆𝑐𝑢𝑟𝑟𝑒𝑛𝑡 ℎ𝑝
ii) Installation cost = ( )(517.5)( )0.82 (2.11 + 𝐹𝑐 )
280 𝜂

𝐼𝑛𝑠𝑡𝑎𝑙𝑙𝑎𝑡𝑖𝑜𝑛 𝐶𝑜𝑠𝑡
iii) Annualized installation cost (in MYR) = x 4 (𝑐𝑢𝑟𝑟𝑒𝑛𝑐𝑦 𝑣𝑎𝑙𝑢𝑒)
3

*M&S = Marshall and Swift inflation index

3. Reactor calculation

Assuming reactor is continuous and thus Plug-Flow Reactor is selected (Level 3 explanation) and
by following the design guidelines provided from Levenspiel (Table 6.6-1(Douglas,1988)).

1
𝐹𝑇 ln( ) 1000
Reactor volume, 𝑉𝑃𝐹𝑅 (𝑚3 ) = 1−𝑥
0.5 𝐶 1 x 3600
𝑘𝐶𝐻
2 𝑇

𝐸𝑎
𝜌𝐻 ( )
2 0.5 1.987x𝑇𝑟,𝑖𝑛 (𝑅)
where, 𝑘 = (1000 ) x𝑒 (obtained from literature)

𝑚𝑜𝑙 𝑦𝐹𝐻 𝐹𝐺 +𝑦𝑃𝐻 𝑅𝐺

𝐶𝐻2 = 𝜌𝐻2 ( 𝑚3 )x 𝑦𝐹𝐻 𝐹𝐺 +𝑦𝑃𝐻 𝑅𝐺 +𝐹𝑇

𝐹𝑇 (1−𝑥)
𝐶𝑇 = 𝜌𝑇 x 𝐹
𝑇 (1−𝑥)+𝑅𝐺 +𝑃𝐺

Assuming reactor is made of Carbon Chromium-Molibdenum with Pout = 34 bar

𝑅𝑀 𝑀&𝑆𝑐𝑢𝑟𝑟𝑒𝑛𝑡
Annual Reactor Cost, = 𝐶𝐼,𝑅𝑒𝑎𝑐𝑡𝑜𝑟 ( )=( ) (7775.3)𝐷1.066 𝐿0.83 (2.18 + 𝐹𝑀 𝐹𝑃 )
𝑦𝑟 280

Where L/D = 5, L =5D

3 2𝑉
D= √5𝜋

EP3 = EP2 – Compressor Cost – Reactor Cost

9
Level 4 SEPARATION SYSTEM STRUCTURE

The reactor effluent stream phase can be differentiated into 3; liquid, (liquid + vapor) and vapor. For each
case, different level 4 separation design should be done.

Case 1: Reactor Effluent Stream Phase: Liquid

Case 2: Reactor Effluent Stream Phase: Two Phases

Case 3: Reactor Effluent Stream Phase: Vapor

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 In Level 4, there are two recovery systems used after Flash separation. Vapor Recovery System (VRS) is to
minimize the benzene loss and Liquid Recovery System (LRS) to recover valuable products such as Benzene from
liquid stream. The function of using Flash is to get the phases to be split. To get both vapor and liquid phases, firstly,
the cooling takes place. The reactor effluent stream has a high temperature (bubble point temperature, 620 ℃) and
thus cooling water is used to cool down it until 35 ℃.

Ki = phase equilibrium constant (360.3)

𝑦𝑖
𝐾𝑖 = (1)
𝑥𝑖

Overall balance, 𝐹 =𝑉+𝐿 (2)

𝐹𝑧𝑖 = 𝑉𝑦𝑖 + 𝐿𝑥𝑖 = 𝑣𝑖 + 𝑙𝑖 (3)

𝑣𝑖 = vapor component flow

𝑙𝑖 = liquid component flow

Degree of freedom, DoF = 3 equations, 3 unknown variables (V, L, Ki) = 3-3 = 0 (can be solved).

Assumption on Perfect Split is no longer used because in this level there are some Benzene and Diphenyl
lost in the vapor stream and Hydrogen & Methane lost in liquid stream.

For vapor phase,

𝑦𝑖
𝐹𝑧𝑖 = 𝑉𝑦𝑖 + 𝐿𝑥𝑖 substitute 𝑥𝑖 =
𝐾𝑖
𝑦 𝐿
𝐹𝑧𝑖 = 𝑉𝑦𝑖 + 𝐿 ( 𝑖 ) = 𝑦𝑖 (𝑉 + ( )) as Ki >>1, 1/Ki ≈ 0
𝐾𝑖 𝐾𝑖
𝑓𝑖
𝑦𝑖 Σ𝑓𝑖
𝑥𝑖 = = where Σ𝑓𝑖 = 𝑉
𝐾𝑖 𝐾𝑖

𝑓𝑖
𝑙𝑖 = 𝐿𝑥𝑖 = Σ𝑓𝐵𝑧, 𝑇𝑜𝑙, 𝐷𝑝 ( )
KiΣ𝑓𝑖

11
For liquid phase,

𝐹𝑧𝑖 = 𝑉𝑦𝑖 + 𝐿𝑥𝑖 substitute 𝑦𝑖 = 𝐾𝑖 𝑥𝑖

𝐹𝑧𝑖 = 𝑉𝐾𝑖 𝑥𝑖 + 𝐿𝑥𝑖 = 𝑥𝑖 (𝑉𝐾𝑖 + 𝐿 ) as Ki <<1, VKi ≈ 0
𝐹𝑧𝑖 𝑓𝑗
Thus,𝑦𝑖 = 𝐾𝑖 𝑥𝑖 = 𝐾𝑖 = where Σ𝑓𝑗 = 𝐿
𝐿 Σf𝑗

𝑓𝑗
𝑣𝑖 = 𝑉𝑦𝑖 𝑣𝑖 = 𝑉𝑦𝑖 = Σ𝑓𝐻2 , 𝐶𝐻4 ( )
Σf𝑗

Some options on Vapor Recovery System can be shown in different cases.

1. If there is some corrosive composition or contaminants harmful to Benzene, VRS (a) should be used.
2. If the main product (Benzene) is wanted to be recovered more, VRS (b) should be done.
3. VRS (c) should be used if both cases applied.

The cost to apply VRS is higher from case 1,2, and 3. After flash column, doing VRS system needs a lot
of cost.

VRS (a) VRS (b)

VRS (c)

f
l
a
s
h

LRS

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