KKEK 2156

DESIGN EXERCISE
DEPARTMENT OF CHEMICAL ENGINEERING
UNIVERSITY OF MALAYA
SESSION 2014/2015, SEMESTER 2

GROUP: 6
LECTURER: DR. BRAHIM SI ALI
NAME OF GROUP MEMBERS

MATRICS NO.

ARUNAN MOHANAN

KEK 120023

NG SAU WEI

KEK 120037

NOOR HANISAH BINTI ABDUL HAMID

KEK 120038

SITI FAIRUZ BINTI

KEK 120049

YONG KUN GUAN

KEK 120064

1.0 INTRODUCTION
Chlorine is a very important raw material in the industry to produce large amount of
chlorine-based products. It is commonly used it the production of plastics, solvents for
dry cleaning and metal degreasing, textiles, insecticides, household cleaning products
and others. In the industry, chlorine is usually produced by the electrolysis of NACl, with
co-product of caustic soda. However, surplus of alkali and deficit of chlorine are the
common problems in the current world. The byproduct, HCl that usually produced from
the process also cause disposal problem to the environment. Thus, many methods have
been proposed in the industry to recover chlorine from hydrogen chloride such as
electrolysis, direct oxidation and Deacon Process. For electrolysis process, there is
always a limitation where the equipment investment and energy consumption are very
high. For direct oxidation, the conversion of HCl is not so efficient and more waste need
to be disposed. As the result, Deacon process become the preferable choice in the
industry.
Deacon process is a catalytic oxidation process, in which HCl is oxidized by
oxygen or air in the presence of CuCl2 catalyst at about 400C to produce chlorine as the
final product. Deacon process usually involves two steps of reaction which are oxidation
and chloridation. The chemical reactions are as follow:

Chloridation: CuO + 2HCl CuCl2 + H2O

H = -28.8 kcal/mol

Oxidation: CuCl2 + 0.5O2 CuO + Cl2

H = 15.0kcal/mol

During chloridation, HCl is contacted with the catalyst at a high temperature.

This step converts the copper oxide to copper chloride with elimination of water. It is
followed by oxidizing step in which the copper chloride is reacted with oxygen to
produce chlorine gas and copper chloride is reconverted back to copper oxide.
In this project, a plant that produces 10,000 metric tons per year of chlorine by
the catalytic oxidation of HCl gas has been proposed. The HCl gas is allowed to react
with air in a fluidized bed reactor containing cupric chloride. The products which
consist of chlorine gas, unreacted hydrogen chloride and humid air are then through a
series of separation and purification process to obtain a very high purity of chlorine gas.
HCl absorbers are designed to separate the impurities from the product gas while HCl
stripper is designed to increase the recovery of Cl2 gas from HCl. Lastly, a dryer is used
to dry the product gas to obtain a pure dry chlorine gas.

2.0 OBJECTIVES
To come up with mass and energy balances for the reaction.
To generate process flow diagram (PFD) by using software such as AutoCAD,
AspenTech etc.
To design the unit operations that have been chosen for the process in terms
of
a. Chemical Engineering design
b. Mechanical Engineering design

3.0 LITERATURE REVIEW

3.1

Physical Properties Data

Molecular Weight
Molar Mass
H20
Cl2
HCl
O2
N2
H2SO4

18.00
71.00
36.50
32.00
28.00
98.08

kmol/kg
kmol/kg
kmol/kg
kmol/kg
kmol/kg
kmol/kg

3.2 Safety issues

3.2.1 Chemical Product

Product Name: Hydrochloric acid

Catalog Codes: SLH1462, SLH3154
CAS#: Mixture.
Synonym: Hydrochloric Acid; Muriatic Acid
Chemical Name: Not applicable.
Chemical Formula: Not applicable
3.2.2 Composition and Information on Ingredients

Name
CAS #
Hydrogen chloride 7647-01-0
Water
7732-18-5

% by Weight
20-38
62-80

Toxicological Data on Ingredients:

Hydrogen chloride: GAS (LC50): Acute: 4701 ppm 0.5 hours [Rat].
3.2.3 Stability and Reactivity Data

Stability: The product is stable.

Instability Temperature: Not available.
Conditions of Instability: Incompatible materials, water
Incompatibility with various substances:
Highly reactive with metals. Reactive with oxidizing agents, organic materials,
alkalis, water.
Corrosivity:
Extremely corrosive in presence of aluminum, of copper, of stainless steel (304),
of stainless steel (316). Non-corrosive in presence of glass.
Special Remarks on Reactivity:
Reacts with water especially when water is added to the product. Absorption of
gaseous hydrogen chloride on mercuric sulfate becomes violent @ 125 deg. C.
Sodium reacts very violently with gaseous hydrogen chloride. Calcium phosphide
and hydrochloric acid undergo very energetic reaction. It reacts with oxidizers
releasing chlorine gas. Incompatible with alkali metals, carbides, borides, metal
oxides, vinyl acetate, acetylides, sulphides, phosphides, cyanides, carbonates.
Reacts with most metals to produce flammable Hydrogen gas. Reacts violently
(moderate reaction with heat of evolution) with water especially when water is
added to the product. Isolate hydrogen chloride from heat, direct sunlight,
alkalies (reacts vigorously), organic materials, and oxidizers (especially nitric
acid and chlorates), amines, metals, copper and alloys (e.g. brass), hydroxides,
zinc (galvanized materials), lithium silicide (incandescence), sulfuric acid
(increase in temperature and pressure) Hydrogen chloride gas is emitted when
this product is in contact with sulfuric acid. Adsorption of Hydrochloric Acid onto
silicon dioxide results in exothermic reaction. Hydrogen chloride causes
aldehydes and epoxides to violently polymerize. Hydrogen chloride or
Hydrochloric Acid in contact with the following can cause explosion or ignition
on contact.
Special Remarks on Corrosivity:
Highly corrosive. Incompatible with copper and copper alloys. It attacks nearly
all metals (mercury, gold, platinum, tantalum, silver, and certain alloys are

exceptions). It is one of the most corrosive of the non-oxidizing acids in contact

with copper alloys. No corrosivity data on zinc, steel. Severe Corrosive effect on
brass and bronze.
Polymerization: Will not occur.
Chlorine is produced for this process, first aid measures should take into
account under certain circumstance especially if there are any leakage in the
chlorine storage. The first aid measures are; after inhalation, after skin contact,
after eye contact, after ingestion with the chlorine gas. The description for the
first aid measure as per stated in the MSDS of chlorine in section 4. Medical
assistance needed if any immediate medical attention. The most important
symptoms are choking, coughing, burning of the throat, and severe irritation of
the upper respiratory tract; additionally, pulmonary edema, bronchitis, and
pneumonitis may result.
Accidental release measure of chlorine gas mainly paid more attention to
the environment by preventing waste from contaminating the surrounding
environment. Prevent soil and water pollution. Dispose of contents/container in
accordance with local/regional/national/international regulations.
Other sections which requires serious attention:
a. Reactivity
No reactivity hazard other than the effects described in sub-sections below.
b. Chemical stability
Stable under normal conditions.
c. Possibility of hazardous reactions
May occur.
Conditions to avoid
Air contact. High temperature. Moisture. Incompatible materials

3.4 Standards
Code of professional conduct is followed before and while designing this plant.
Hold paramount the safety, health and welfare of the public and protect
the environment in performance of the professional duties.
Accept responsibility for the actions, seek and heed critical review of their
work and offer objective criticism of the work of others.
Issue statements or present information only in an objective and truthful
manner.

4.0 PROCESS FLOW DIAGRAM

5.0 MASS & ENERGY BALANCE

5.1 Mass Balance
Mass balances are carried out to determine the amount of input feed required to
achieve the desired production rate and purity. It is also to cross check whether
the Aspen Plus simulation software give a reasonable result. Each stream is
calculated manually and is compared with the software result.
Methodology
Firstly, the desired production rate and product purity is fixed. Then overall mass
balance is carried out to roughly determine the input flow. Next, material balance
is carried out at the outlet unit operation and then to every unit operation. All
mass or mole balance is carried out using the following formula. In some cases,
assumptions are made to simplify the calculation and thus some errors may arise
from that. The following show the general mass balance equation:
General mole/mass balance[7]
Input + generation output consumption = accumulation
For reactive system:
Input + generation output consumption = accumulation =0
Output = input + generation - consumption
For non-reactive system:
Input + generation output consumption = accumulation
output = input
General assumptions made:

Process at steady-state accumulation = 0

Reactions occurs in reactor

No heat loss

No side reactions occur

Isothermal condition

5.1.1 Fluidized Bed Reactor

In this process, air is used as the limiting reactant, (controlled the flow rate), as
some the
will be recycle back to the reactor from expeller. (HCl in excess)
Therefore, based on the stoichiometry calculation;
( )

2(

2(

( )

Reactant flow (Stream no. 5)

The desired 2 production rate is 17.61 kmol/h, by considering 80% oxygen
conversion therefore mathematically, about 11.02 kmol/h of 2 needed.

Product Flow (Stream no. 6)

:
2

2:

2:

GAS INLET to mixer (STREAM 1)

GAS INLET to mixer (STREAM 2)

Total molar rate=

Total mass rate=
Total mole fraction=
Total mass fraction=

38.67 kmol/h
1411.46 kg/h
1.0000
1.0000

HCl(g)

38.67 kmol/h O2 (g)

1411.46 kg/h
1.0000
1.0000

Molar rate
Mass rate
Mole frac
Mass frac

11.02 kmol/h
352.64 kg/h
0.2100
0.2099

N2 (g)

Molar rate
Mass rate
Mole frac
Mass frac

47.40 kmol/h
1327.76 kg/h
0.7900
0.7901

Molar rate
Mass rate
Mole frac
Mass frac

GAS OUTLET from mixer (STREAM 3)

Total molar rate=
97.09 kmol/h
Total mass rate= 3091.30 kg/h
Total mole
fraction= 1.0000
Total mass
fraction= 1.0000
HCl(g)

O2
(g)

Molar rate
Mass rate
Mole frac
Mass frac

Molar rate
Mass rate
Mole frac

38.67 kmol/h
1411.46 kg/h
0.3983
0.4566

11.02 kmol/h
352.64 kg/h
0.1135

Total molar rate=

Total mass rate=
Total mole fraction=
Total mass fraction=

58.44 kmol/h
1680.40 kg/h
1.0000
1.0000

GAS recycle from expeller (STREAM 4)

Total molar rate=
36.61 kmol/h
Total mass rate= 1324.32 kg/h
Total mole
fraction= 1.0000
Total mass
fraction= 1.0000
HCl(g)

H2O
(g)

Molar rate
35.42 kmol/h
Mass rate 1292.83 kg/h
Mole frac 0.9747
Mass frac 0.9762

Molar rate
Mass rate
Mole frac

1.00 kmol/h
18.00 kg/h
0.0200

Mass frac

N2 (g)

Molar rate
Mass rate
Mole frac
Mass frac

0.1141

47.40 kmol/h
1327.20 kg/h
0.4882
0.4293

GAS INLET to reactor (STREAM 5)

Total molar rate= 133.70 kmol/h
Total mass rate= 4415.62 kg/h
Total mole fraction=

1.0000

Total mass fraction=

1.0000

HCl(g)

H2O
(g)

Molar rate
74.09 kmol/h
Mass rate 2704.30 kg/h
Mole frac 0.5553
Mass frac 0.6124

Mass frac
Cl2
(g)

Molar rate
Mass rate
Mole frac
Mass frac

0.0136

0.19 kmol/h
13.49 kg/h
0.0052
0.0100

GAS OUTLET from reactor (STREAM 6)

Total molar rate= 125.24 kmol/h
Total mass rate= 4422.22 kg/h
Total mole
fraction= 1.0000
Total mass
fraction= 1.0000
HCl(g)

H2O
(g)

Molar rate
38.83 kmol/h
Mass rate 1417.30 kg/h
Mole frac 0.3100
Mass frac 0.3205

Molar rate
Mass rate
Mole frac
Mass frac

1.00 kmol/h
18.00 kg/h
0.0055
0.0041

Molar rate
Mass rate
Mole frac
Mass frac

18.97 kmol/h
341.46 kg/h
0.1515
0.0772

Cl2 (g)

Molar rate
Mass rate
Mole frac
Mass frac

0.19 kmol/h
13.49 kg/h
0.0014
0.0031

Cl2 (g)

Molar rate
17.82 kmol/h
Mass rate 1265.22 kg/h
Mole frac 0.1423
Mass frac 0.2861

N2(g)

Molar rate
Mass rate
Mole frac

47.4 kmol/h
1327.2 kg/h
0.3552

N2(g)

Molar rate
Mass rate
Mole frac

47.4 kmol/h
1327.2 kg/h
0.3785

Mass frac

O2(g)

Molar rate
Mass rate
Mole frac
Mass frac

0.3006

11.02 kmol/h
352.64 kg/h
0.0824
0.0799

Mass frac

O2(g)

Molar rate
Mass rate
Mole frac
Mass frac

0.3001

2.22 kmol/h
71.04 kg/h
0.0177
0.0161

5.1.2 1st stage HCl Absorber

PACKED COLUMN SCRUBBER

(STREAM 12)
LIQ INLET after recycle
Total molar rate=
173.99 kmol/h
Total mass rate= 3830.30 kg/h
Total mole fraction=
1.0000
Total mass fraction=
1.0000
HCl(l)

H2O (l)

Molar rate
Mass rate
Mole frac
Mass frac
Volume rate

kmol/h
kg/h

Concentration

37.76
1378.09
0.2170
0.3598
845.45
4.47E02

Molar rate
Mass rate
Mole frac
Mass frac
Volume rate
Concentration

136.23
2452.22
0.7830
0.6402
2.46
55.4444

kmol/h
kg/h

(STREAM 10)
ACID FRESH FEED before recycle
Total molar rate=
Total mass rate=
Total mole fraction=
Total mass fraction=
HCl(l)

m3/h

Molar rate
Mass rate
Mole frac
Mass frac
Volume rate

mol/L

Concentration

4.47E-02 mol/L

Molar rate
Mass rate
Mole frac
Mass frac
Volume rate
Concentration

46.41
835.46
0.9913
0.9826
0.84
55.4444

H2O
(l)

m3/h
mol/L

(STREAM 7)
GAS INLET FROM REACTOR
Total molar rate=
Total mass rate=
Total mole fraction=
Total mass fraction=
HCl(g)

H2O (g)

Molar rate
Mass rate
Mole frac
Mass frac
Volume rate
Concentration
Molar rate
Mass rate

0.41 kmol/h
14.81 kg/h
0.0087
0.0174
9.09 m3/h

kmol/h
kg/h

m3/h
mol/L

(STREAM 13)
GAS OUTLET TO 2ND ABSORBER

125.24 kmol/h
4386.76 kg/h
1.0000
1.0000
38.83
1417.44
0.3101
0.3231
1762.99
0.0220

46.82 kmol/h
850.27 kg/h
1.0000
1.0000

kmol/h
kg/h

Total molar rate=

Total mass rate=
Total mole fraction=
Total mass fraction=
HCl(g)

m3/h
mol/L

18.97 kmol/h
341.38 kg/h

H2O (g)

Molar rate
Mass rate
Mole frac
Mass frac
Volume rate
Concentration
Molar rate
Mass rate

87.28 kmol/h
3250.18 kg/h
1.0000
1.0000
14.34
523.25
0.1643
0.1610
342.44
0.0419

kmol/h
kg/h

m3/h
mol/L

5.50 kmol/h
98.99 kg/h

Mole frac
Mass frac
Volume rate
Concentration
Cl2 (g)

N2(g)

O2(g)

0.1514
0.0778
424.60 m3/h
0.0447 mol/L

Molar rate
Mass rate
Mole frac
Mass frac
Volume rate
Concentration

17.82
1265.22
0.1423
0.2884
422.59
0.0422

kmol/h
kg/h

Molar rate
Mass rate
Mole frac
Mass frac
Volume rate
Concentration

47.4
1327.2
0.3785
0.3025
1061.25
0.0447

kmol/h
kg/h

Molar rate
Mass rate
Mole frac
Mass frac
Volume rate
Concentration

2.22
35.52
0.0177
0.0081
24.86
0.0893

kmol/h
kg/h

HCl(l)

H2O (l)

Molar rate
Mass rate
Mole frac
Mass frac
Volume rate
Concentration
Molar rate

N2(g)

m3/h
mol/L

m3/h
mol/L

211.95 kmol/h
4966.73 kg/h
1.0000
1.0000
62.25
2272.13
0.2937
0.4575
1393.94
0.0447

Cl2 (g)

m3/h
mol/L

(STREAM 8)
LIQ OUTLET FROM BOTTOM
Total molar rate=
Total mass rate=
Total mole fraction=
Total mass fraction=

Mole frac
Mass frac
Volume rate
Concentration

kmol/h
kg/h

m3/h
mol/L

149.70 kmol/h

O2(g)

0.0630
0.0305
123.13 m3/h
0.0447 mol/L

Molar rate
Mass rate
Mole frac
Mass frac
Volume rate
Concentration

17.82
1265.22
0.2042
0.3893
422.59
0.0422

kmol/h
kg/h

Molar rate
Mass rate
Mole frac
Mass frac
Volume rate
Concentration

47.4
1327.2
0.5431
0.4083
1061.25
0.0447

kmol/h
kg/h

Molar rate
Mass rate
Mole frac
Mass frac
Volume rate
Concentration

2.22
35.52
0.0254
0.0109
24.86
0.0893

kmol/h
kg/h

m3/h
mol/L

m3/h
mol/L

m3/h
mol/L

Mass rate
Mole frac
Mass frac
Volume rate
Concentration

2694.60 kg/h
0.7063
0.5425
2.70 m3/h
55.4444 mol/L

(STREAM 15)
PURGE TO EXPELLER
Total molar rate=
Total mass rate=
Total mole fraction=
Total mass fraction=
HCl(l)

H2O (l)

(STREAM 9)
RECYCLE BACK TO SCRUBBER

84.78 kmol/h
1986.69 kg/h
1.0000
1.0000

Molar rate
Mass rate
Mole frac
Mass frac
Volume rate
Concentration

24.90
908.85
0.2937
0.4575
557.58
0.0447

kmol/h
kg/h

Molar rate
Mass rate
Mole frac
Mass frac
Volume rate
Concentration

59.88
1077.84
0.7063
0.5425
1.08
55.4444

kmol/h
kg/h

Total molar rate=

Total mass rate=
Total mole fraction=
Total mass fraction=
HCl(l)

m3/h
mol/L

m3/h
mol/L

H2O (l)

127.17 kmol/h
2980.04 kg/h
1.0000
1.0000

Molar rate
Mass rate
Mole frac
Mass frac
Volume rate
Concentration

37.35
1363.28
0.2937
0.4575
836.37
0.0447

kmol/h
kg/h

Molar rate
Mass rate
Mole frac
Mass frac
Volume rate
Concentration

89.82
1616.76
0.7063
0.5425
1.62
55.4444

kmol/h
kg/h

m3/h
mol/L

m3/h
mol/L

5.1.3 Stripping Column

MIXER 3
(STREAM 15)
IN FROM SPLITTER
Total molar rate=
85 kmol/h
Total mass rate=
1987 kg/h

(STREAM 23)
IN FROM RECYCLE ( 36%HCL)
Total molar rate=
169 kmol/h
Total mass rate=
3741 kg/h
Cl2 (g)

HCl(aq)

H2O (l)

Molar rate
Mass rate
Mole frac
Molar rate
Mass rate
Mole frac

25
909
0.2937
60
1078
0.7063

kmol/h
kg/h

HCl(aq)

kmol/h
kg/h

H2O (l)

Molar rate
Mass rate
Mole frac
Molar rate
Mass rate
Mole frac
Molar rate
Mass rate
Mole frac

0.1897
13
0.0011
37
1354
0.2192
132
2374
0.7797

kmol/h
kg/h
kmol/h
kg/h
kmol/h
kg/h

(STREAM 16)
MIXED OUTLET
Total molar rate=
Total mass rate=
Cl2 (g)

HCl(aq)

H2O (l)

Molar rate
Mass rate
Mole frac
Molar rate
Mass rate
Mole frac
Molar rate
Mass rate
Mole frac

254 kmol/h
5728 kg/h
0.1897
13
0.0007
62
2262
0.2441
192
3452
0.7552

kmol/h
kg/h
kmol/h
kg/h
kmol/h
kg/h

EXPELLER
(STREAM 16)
LIQUID FEED
Total molar rate=
254 kmol/h
Total mass rate=
5728 kg/h

Cl2 (g)

Molar
rate
Mass rate

0.1897 kmol/h
13 kg/h

(STREAM 14)
STEAM IN
Total molar rate=
Total mass rate=

Steam at 200psig

19 kmol/h
335 kg/h

HCl(aq)

H2O (l)

Mole frac
Molar
rate
Mass rate

0.0007

Mole frac
Molar
rate
Mass rate
Mole frac

0.2441

From steam table:

62 kmol/h
2262 kg/h

Temp of Sat. Steam

Latent Heat of Steam
Specific Enthalpy of Sat.
Steam
Specific Enthalpy of Sat.
Water

192 kmol/h
3452 kg/h
0.7552

(STREAM 19)
OUT, LIQUID (EFFLUENT)
Total molar rate=
218 kmol/h
Total mass rate=
4409 kg/h

Molar rate
Mass rate
Mole frac

27 kmol/h
970 kg/h
0.1221

H2O (l)

Molar rate
Mass rate
Mole frac

191 kmol/h
3439 kg/h
0.8779

2791

kJ/kg

842

kJ/kg

(STREAM 17)
OUT, VAPOR ( RECYCLE)
Total molar rate=
51 kmol/h
Total mass rate=
1589 kg/h
Cl2 (g)

HCl(aq)

198 C
1949 kJ/kg

HCl(g)

H2O
(g)

Molar rate
Mass rate
Mole frac
Molar rate
Mass rate
Mole frac

0.1858
13
0.0036
35
1293
0.6899

kmol/h
kg/h

Molar rate
Mass rate
Mole frac

16 kmol/h
283 kg/h
0.3065

kmol/h
kg/h

5.1.4 2nd stage HCl Absorber

Mass Balance for a HCl Absorber

To Dryer
(Stream 24)

From Scrubber
(Stream 20)

Molar flow Rate (kmol/hr)

Molar flow Rate (kmol/hr)

Total = 24

Total (20 ) = 217.64

= m*x

= m*y

= 26.57

2 = m*z
2
m*a

)2

=0

2 = 191.06
HCl Absorber

=0

=0

From Scrubber
(Stream 13)

To Splitter 2
(Stream 21)

Molar flow Rate (kmol/hr)

Molar flow Rate (kmol/hr)

Total (13 ) = 87.28

Total (21 ) = 187.65

= 17.82

= 0.2064

= 14.34

= 40.89

2 = 5.5

2 = 146.56

= 47.4

=0

= 2.22

=0

Assumptions
1. Absorption is a non-reactive process, no generation of mass occurs.
2. No consumption of mass and accumulation of mass.
3. Only physical absorption occurs in the packed column HCl absorber
The overall mass balance has been reduced to the simplified form of:

Input Mass Output Mass = 0

Input Mass = Output Mass
Specification
The mass fraction of HCl leaving to splitter 2(Stream 21) is 36% by mass or 22% by mole

In the process,
13

20

24
24

24

Component Mass Balance

2:

17.82 =

24

24

x = 0.1502
HCl:
14.34 + 26.5735 =

24

24

y = 0.000015

21

5.5 + 191.0641 =

24

24

z = 0.4265

47.4 =

24

24

a = 0.4043

2.22 =

24

Molar flow Rate (kmol/hr)

Hence, the total molar flow rate and molar flow rate of each component flows to the
dryer is calculated. In summary,

Total =

24

= 117.2353kmol/hr
= 17.6136 kmol/hr

= 0.001712 kmol/hr
2

= 50 kmol/hr

= 47.4 kmol/hr

= 2.22 kmol/hr

At Inlet:
HCL ABSORBER
INLET(FROM SCRUBBER)
STREAM 13

INLET(FROM COOLER 2)
STREAM 20

Cl2

Molar Flow Rate

Mass Flow Rate
Mole Fraction

18
1276
0.2042

kmol/hr
kg/h

Cl2

Molar Flow Rate

Mass Flow Rate
Mole Fraction

0
0
0

kmol/hr
kg/h

HCL

Molar Flow Rate

Mass Flow Rate
Mole Fraction

14
523
0.1643

kmol/hr
kg/h

HCL

Molar Flow Rate

Mass Flow Rate
Mole Fraction

27
969
0.1221

kmol/hr
kg/h

H2O

Molar Flow Rate

Mass Flow Rate
Mole Fraction

6
99
0.063

kmol/hr
kg/h

H2O

Molar Flow Rate

Mass Flow Rate
Mole Fraction

191
3439
0.8779

kmol/hr
kg/h

N2

Molar Flow Rate

Mass Flow Rate
Mole Fraction

47
1327
0.5431

kmol/hr
kg/h

N2

Molar Flow Rate

Mass Flow Rate
Mole Fraction

0
0
0

kmol/hr
kg/h

O2

Molar Flow Rate

Mass Flow Rate
Mole Fraction

2
71.025
0.0254

kmol/hr
kg/h

O2

Molar Flow Rate

Mass Flow Rate
Mole Fraction

0
0
0

kmol/hr
kg/h

Total

Molar Flow Rate

Mass Flow Rate

87
3296

kmol/hr
kg/h

Total

Molar Flow Rate

Mass Flow Rate

218
4408

kmol/hr
kg/h

At outlet:
HCL ABSORBER
OUTLET(BOTTOM)
STREAM 21

OUTLET(TOP)
STREAM 24

Cl2

Molar Flow Rate

Mass Flow Rate
Mole Fraction

0.21
15
0.0011

kmol/hr
kg/h

Cl2

Molar Flow Rate

Mass Flow Rate
Mole Fraction

18
1249
0.1502

kmol/hr
kg/h

HCL

Molar Flow Rate

Mass Flow Rate
Mole Fraction

41
1490
0.2179

kmol/hr
kg/h

HCL

Molar Flow Rate

Mass Flow Rate
Mole Fraction

0
0.06
0

kmol/hr
kg/h

H2O

Molar Flow Rate

Mass Flow Rate
Mole Fraction

147
2638
0.781

kmol/hr
kg/h

H2O

Molar Flow Rate

Mass Flow Rate
Mole Fraction

50
900
0.4265

kmol/hr
kg/h

N2

Molar Flow Rate

Mass Flow Rate
Mole Fraction

0
0
0

kmol/hr
kg/h

N2

Molar Flow Rate

Mass Flow Rate
Mole Fraction

47
1422
0.4043

kmol/hr
kg/h

O2

Molar Flow Rate

Mass Flow Rate
Mole Fraction

0
0
0

kmol/hr
kg/h

O2

Molar Flow Rate

Mass Flow Rate
Mole Fraction

2
71
0.0189

kmol/hr
kg/h

Total

Molar Flow Rate

Mass Flow Rate

188
4143

kmol/hr
kg/h

Total

Molar Flow Rate

Mass Flow Rate

117
2149

kmol/hr
kg/h

Mass Balance for Splitter 2

Assumptions:
The purge-to-recycle ratio is 1:9 in which portion of 9 is being recycled as in stream 23
and portion of 1 flows exits as the product.

At inlet & Outlet(Recycle):

SPLITTER 2
INLET
STREAM 21

OUTLET(RECYCLE)
STREAM 23

Cl2

Molar Flow Rate

Mass Flow Rate
Mole Fraction

0.21
15
0.219

kmol/hr
kg/h

Cl2

Molar Flow Rate

Mass Flow Rate
Mole Fraction

0.2
3.34
0.0011

kmol/hr
kg/h

HCL

Molar Flow Rate

41
Mass Flow Rate 1490
Mole Fraction 0.2179

kmol/hr
kg/h

HCL

Molar Flow Rate

Mass Flow Rate
Mole Fraction

37
1341
0.2179

kmol/hr
kg/h

H2O

Molar Flow Rate

Mass Flow Rate
Mole Fraction

147
2638
0.781

kmol/hr
kg/h

H2O

Molar Flow Rate

Mass Flow Rate
Mole Fraction

132
2374
0.781

kmol/hr
kg/h

N2

Molar Flow Rate

Mass Flow Rate
Mole Fraction

0
0
0

kmol/hr
kg/h

N2

Molar Flow Rate

Mass Flow Rate
Mole Fraction

0
0
0

kmol/hr
kg/h

O2

Molar Flow Rate

Mass Flow Rate
Mole Fraction

0
0
0

kmol/hr
kg/h

O2

Molar Flow Rate

Mass Flow Rate
Mole Fraction

0
0
0

kmol/hr
kg/h

Total

Molar Flow Rate

188

kmol/hr

Total

Molar Flow Rate

169

kmol/hr

Mass Flow Rate

4143

kg/h

At outlet:
Splitter 2
Outlet(Product)
Stream 22
Cl2 Molar Flow Rate
0
Mass Flow Rate
0
Mole Fraction
0.0011

kmol/hr
kg/h

HCL Molar Flow Rate

Mass Flow Rate
Mole Fraction

4
149
0.2179

kmol/hr
kg/h

H2O Molar Flow Rate

Mass Flow Rate
Mole Fraction

15
264
0.781

kmol/hr
kg/h

N2 Molar Flow Rate

Mass Flow Rate
Mole Fraction

0
0
0

kmol/hr
kg/h

O2 Molar Flow Rate

Mass Flow Rate
Mole Fraction

0
0
0

kmol/hr
kg/h

Total Molar Flow Rate

Mass Flow Rate

19
414

kmol/hr
kg/h

Mass Flow Rate

3716

kg/h

5.1.4 Dryer
COOLER
IN

OUT(TO DRYER)

Total mass rate=

Total mole rate=

3558.97 kg/hr
117.37 kmol/hr

Total mass rate=

Total mole rate=

3558.97 kg/hr
117.69 kmol/hr

H2O

Mass rate =
Mole rate=
Mole fraction=

900.00 kg/hr
50.00 kmol/hr
0.43

H2O

Mass rate =
Mole rate=
Mole fraction=

900.00 kg/hr
50.00 kmol/hr
0.42

Cl2

Mass rate =
Mole rate=
Mole fraction=

1260.87 kg/hr
17.76 kmol/hr
0.15

Cl2

Mass rate =
Mole rate=
Mole fraction=

1260.87 kg/hr
17.76 kmol/hr
0.15

HCl

Mass rate =
Mole rate=
Mole fraction=

0.06 kg/hr
0.00 kmol/hr
0.00

HCl

Mass rate =
Mole rate=
Mole fraction=

0.06 kg/hr
0.00 kmol/hr
0.00

O2

Mass rate =
Mole rate=
Mole fraction=

71.04 kg/hr
2.22 kmol/hr
0.02

O2

Mass rate =
Mole rate=
Mole fraction=

71.04 kg/hr
2.54 kmol/hr
0.02

N2

Mass rate =
Mole rate=
Mole fraction=

1326.99 kg/hr
47.39 kmol/hr
0.40

N2

Mass rate =
Mole rate=
Mole fraction=

1326.99 kg/hr
47.39 kmol/hr
0.40

DRYER
IN(COOLER)

OUT(SULFURIC ACID)
30% H2SO4
Total mass rate= 1297.00 kg/hr
Total mole rate=
54.41 kmol/hr

Total mass rate=

Total mole rate=

3558.97 kg/hr
117.69 kmol/hr

H2O

Mass rate =
Mole rate=
Mole fraction=

900.00 kg/hr
50.00 kmol/hr
0.42

H2O

Mass rate =
Mole rate=
Mole fraction=

907.90 kg/hr
50.44 kmol/hr
0.93

Cl2

Mass rate =
Mole rate=
Mole fraction=

1260.87 kg/hr
17.76 kmol/hr
0.15

HCl

Mass rate =
Mole rate=
Mole fraction=

389.10 kg/hr
3.97 kmol/hr
0.07

HCl

Mass rate =
Mole rate=
Mole fraction=

0.06 kg/hr
0.00 kmol/hr
0.00

O2

Mass rate =
Mole rate=
Mole fraction=

71.04 kg/hr
2.54 kmol/hr
0.02

N2

Mass rate =
Mole rate=
Mole fraction=

1326.99 kg/hr
47.39 kmol/hr
0.40

1ST DRYER COLUMN

OUT (SULFURIC ACID + H2O)
70% H2SO4
Total mass rate= 555.86 kg/hr
Total mole rate=
13.23 kmol/hr

OUT(Cl2)
Total mass rate=
Total mole rate=

2817.82 kg/hr
76.52 kmol/hr

HCl

Mass rate =
Mole rate=
Mole fraction=

166.76 kg/hr
9.26 kmol/hr
0.70

H2O

Mass rate =
Mole rate=
Mole fraction=

158.86 kg/hr
8.83 kmol/hr
0.12

H2O

Mass rate =
Mole rate=
Mole fraction=

389.10 kg/hr
3.97 kmol/hr
0.30

Cl2

Mass rate =
Mole rate=
Mole fraction=

1260.87 kg/hr
17.76 kmol/hr
0.23

HCl

Mass rate =
Mole rate=
Mole fraction=

0.06 kg/hr
0.00 kmol/hr
0.00

O2

Mass rate =
Mole rate=
Mole fraction=

71.04 kg/hr
2.54 kmol/hr
0.03

N2

Mass rate =
Mole rate=
Mole fraction=

1326.99 kg/hr
47.39 kmol/hr
0.62

2ND DRYER COLUMN

OUT(SULFURIC ACID + WATER)
OUT(Cl2)
98 % H2SO4
Total mass rate= 397.04 kg/hr
Total mass rate= 2659.01 kg/hr
Total mole rate=
4.41 kmol/hr
Total mole rate=
67.69 kmol/hr
HCl

Mass rate =

389.10 kg/hr

H2O

Mass rate =

0.04 kg/hr

H2O

Mole rate=
Mole fraction=

3.97 kmol/hr
0.90

Mass rate =
Mole rate=
Mole fraction=

7.94 kg/hr
0.44 kmol/hr
0.10

Mole rate=
Mole fraction=

0.00 kmol/hr
0.00

Cl2

Mass rate =
Mole rate=
Mole fraction=

1260.87 kg/hr
17.76 kmol/hr
0.23

HCl

Mass rate =
Mole rate=
Mole fraction=

0.06 kg/hr
0.00 kmol/hr
0.00

O2

Mass rate =
Mole rate=
Mole fraction=

71.04 kg/hr
2.54 kmol/hr
0.04

N2

Mass rate =
Mole rate=
Mole fraction=

1326.99 kg/hr
47.39 kmol/hr
0.62

LIQUEFACTION /COMPRESSION
INLET
Total mass rate=
Total mole rate=

2659.01 kg/hr
67.69 kmol/hr

H2O

Mass rate =
Mole rate=
Mole fraction=

0.04 kg/hr
0.00 kmol/hr
0.00

Cl2

Mass rate =
Mole rate=
Mole fraction=

HCl

OUTLET
TO LIQUID Cl2 (0.00005% RESIDUE)
Total mass rate= 1261.00 kg/hr
Total mole rate=
17.76 kmol/hr
H2O

Mass rate =
Mole rate=
Mole fraction=

0.00 kg/hr
0.00 kmol/hr
0.00

1260.87 kg/hr
17.76 kmol/hr
0.26

Cl2

Mass rate =
Mole rate=
Mole fraction=

1260.87 kg/hr
17.76 kmol/hr
1.00

Mass rate =
Mole rate=
Mole fraction=

0.06 kg/hr
0.00 kmol/hr
0.00

HCl

Mass rate =
Mole rate=
Mole fraction=

0.05 kg/hr
0.00 kmol/hr
0.00

O2

Mass rate =
Mole rate=
Mole fraction=

71.04 kg/hr
2.54 kmol/hr
0.04

O2

Mass rate =
Mole rate=
Mole fraction=

0.00 kg/hr
0.00 kmol/hr
0.00

N2

Mass rate =
Mole rate=
Mole fraction=

1326.99 kg/hr
47.39 kmol/hr
0.70

N2

Mass rate =
Mole rate=
Mole fraction=

0.07 kg/hr
0.00 kmol/hr
0.00

TO SNIFF GAS
Total mass rate=
Total mole rate=

1398.01 kg/hr
49.93 kmol/hr

H2O

Mass rate =
Mole rate=
Mole fraction=

0.04 kg/hr
0.00 kmol/hr
0.00

Cl2

Mass rate =
Mole rate=
Mole fraction=

0.00 kg/hr
0.00 kmol/hr
0.00

HCl

Mass rate =
Mole rate=
Mole fraction=

0.01 kg/hr
0.00 kmol/hr
0.00

O2

Mass rate =
Mole rate=
Mole fraction=

71.04 kg/hr
2.54 kmol/hr
0.05

N2

Mass rate =
Mole rate=
Mole fraction=

1326.92 kg/hr
47.39 kmol/hr
0.95

5.2 Energy Balance

5.2.1 Fluidized Bed Reactor
2

Appendix B.2 (Elementary Principle of Chemical Processes)

Components
HCl (g)
Cl2 (g)
H2O (g)
O2 (g)
N2 (g)

a
0.02913
0.0336
0.03346
0.0291
0.029

b
-1.34E-06
1.37E-05
6.88E-06
1.16E-05
2.20E-06

c
9.72E-09
-1.61E-08
7.60E-09
-6.08E-09
5.72E-09

d
-4.34E-12
6.47E-12
-3.59E-12
1.31E-12
-2.87E-12

At mixer:
Stream 1

(contains HCl only)

20

25

Stream 2

(contains O2 and N2)

20

25

20

,2

Stream 3

,2

25

(contains HCl, O2 and N2)

20

25

20

25

,2

20
25

,2

At reactor:

Reactants

Tref (C)

molar flow
rate, kmol/h

Enthalpy,
kJ/kmol

32
32
32
32
32

25
25
25
25
25

74.09
0.19
1
11.02
47.4

194.1
226.5
224.3
196.2
193.4

Heat of
reactant,
kJ/h
14380.87
43.04
163.74
2162.12
9167.16
25916.93

Temperature,
(C)

Tref (C)

molar flow
rate, kmol/h

Enthalpy,
kJ/kmol

350
350
350
350
350

25
25
25
25
25

38.83
17.82
18.97
2.22
47.4

8029.4
9718.9
9570
8470
8120

311781.6
173190.8
181542.9
18803.4
384888
1070206.7

molar flow
rate,
kmol/h

Enthalpy,
kJ/kmol

Heat of
cool in, kJ/h

38.83
17.82
18.97
2.22
47.4

8029.4
9718.9
9570
8470
8120

311781.6
173190.8
181542.9
18803.4
384888

HCl
Cl2
H2O
O2
N2
total

Temperature,
(C)

HCl
H2O
O2
N2
TOTAL

Products

17.61(-29340)
= -516677.4

Heat of
product,
kJ/h

kJ/h

(
=

527612.37 kJ/h

At Cooler 1:
COOL IN
HCl
Cl2
H2O
O2
N2

Temperature,
(C)

Tref (C)

350
350
350
350
350

25
25
25
25
25

TOTAL

COOL OUT

HCl
Cl2
H2O
O2
N2
TOTAL

1070206.7
Temperature,
(C)

Tref (C)

molar flow
rate,
kmol/h

Enthalpy,
kJ/kmol

65
65
65
65
65

25
25
25
25
25

38.83
17.82
18.97
2.22
47.4

3054
3628
3575
3145
3067

1070206.7

Cooling water is used as the coolant, which is at 24C and flows at 25 kg/h.
The final temperature of the cooling water,

(

)(

Heat of
cool out,
kJ/h
118586.8
64651
67817.8
6981.9
145375.8
403413.3

5.2.2 1st stage HCl Absorber

Constant values for calculation of specific heat capacities (Table B2):
, ( )
A
B

HCl (g)
2.91E-02
-1.34E-06

C
D

9.72E-09
-4.34E-12

H2O (l)
7.540E-02

H2O (g)
3.346E-02
6.880E-06

Cl2 (g)
3.360E-02
1.367E-05

N2 (g)
2.900E-02
2.199E-06

7.604E-09
-3.593E-12

-1.607E-08
6.473E-12

5.723E-09
-2.871E-12

3
O2 (g)
2.910E-02
1.158E-05
-6.076E09
1.311E-12

Source: Felder, R. & Rousseau, R. Elementary Principles of Chemical Processes (3rd ed.).

Calculation of specific enthalpy at different temperature streams:

, ( )

Stream

T(C)

12
7
8
13

20
65
45
50

Specific enthalpy, H (kJ/mol)

HCl (g)
H2O (l)
H2O (g)
Cl2 (g)
N2 (g)
O2 (g)
-1.455E-3.770E01
01
1.164E+00 3.016E+00 1.351E+00 1.367E+00 1.164E+00 1.184E+00
5.819E-01 1.508E+00
7.273E-01 1.885E+00 8.429E-01 8.522E-01 7.273E-01 7.381E-01

Specific heat capacity values for HCl acid at varying compositions & temperature:

Source: Perry's Chemical Engineering Handbook

Conversion calculation of specific heat capacity for HCl acid:
1kcal = 4.184 kJ

Streams
12
8

T(C)
20
45

Specific heat capacity

kcal/kg.C
kJ/kg.C
0.591
2.472744
2.6

Mol% HCl
20
30

kJ/kg
-12.36372
52

Heat of evaporation of water: 2257 kJ/kg

Tref= 25 C = 298 K
Source: Steam table pg 643 Felder, R. & Rousseau, R. Elementary Principles of Chemical

Estimation of heat of vaporization of water at 65 C & 50 C (Stream 7 & 13 respectively):

Watsons Correlation:
(2 )

Tc
T1
T2
Hv(T1)
Hv(T2)

647.4
373
338
2257
2362.34

(1 )

K
K
K
kJ/kg
kJ/kg

2
1

0 38

Tc
T1
T2
Hv(T1)
Hv(T2)

647.4
373
323
2257
2405.23

K
K
K
kJ/kg
kJ/kg

Dew point calculation at Stream 7 (gas inlet):

( )

H2O (g)
HCl (g)
N2 (g)
O2 (g)
Cl2 (g)

A
3.55959
4.57389
3.7362
3.9523
4.28814

B
643.748
868.358
264.651
340.024
969.992

C
-198.043
1.754
-6.788
-4.144
-12.791

Psat
0.152832
117.7305
899.703
902.0824
23.43327

y
0.1514
0.3101
0.3785
0.0177
0.1423
1

P * yi / Pi(sat) +=

1.0000

By iteration calculation in Excel, the dew point temperature for Stream 7:

So, stream 7 can be at any temperature above 55 C (dew point) to remain in gas phase.
It is decided that Stream 7 will operate at 65 C.

Dew point calculation at Stream 7 (gas inlet):

H2O (g)
HCl (g)
N2 (g)
O2 (g)
Cl2 (g)

A
3.55959
4.57389
3.7362
3.9523
4.28814

B
C
Psat
643.748 -198.043 0.063878
868.358
1.754 96.23644
264.651
-6.788 843.3884
340.024
-4.144 831.2791
969.992 -12.791 18.3285

P * yi / Pi(sat) +=

y
0.0630
0.1643
0.5431
0.0254
0.2042
1

1.0000

Similarly, by iteration calculation, the resulting temperature:

So, Stream 13 can be operated at any temperature above 40 C (dew point) to remain in gas
phase.
It is decided that Stream 13 will be operated at 55C.
Initially, it is assumed that the packed column scrubber is ADIABATIC. So the energy balance
equation is reduced to:

PACKED COLUMN HCl ABSORBER

GAS INLET (STREAM 7)
LIQ INLET (STREAM 12)
Temperature=
HCl(l)

H2O (l)

Mass rate
Enthalpy

Molar rate
Enthalpy

20 C
1378.09 kg/hr
-17038.29 kJ/hr
-4.73286 kW
136.23 kmol/h
-0.05136 kJ/hr
-0.00001 kW

Temperature=

65 C

HCl(g)

Molar rate
Enthalpy

38.834 kmol/h
0.04519 kJ/hr
1.255E-05 kW

H2O (g)

Mass rate
Molar rate
Enthalpy

341.38
18.97
8.065E+05
224.01549

Cl2 (g)

Molar rate
Enthalpy

17.82 kmol/hr
0.02436 kJ/hr
6.768E-06 kW

N2(g)

Molar rate
Enthalpy

47.40 kmol/hr
5.519E-02 kJ/hr
1.533E-05 kW

kg/h
kmol/hr
kJ/hr
kW

O2(g)

Molar rate
Enthalpy

2.22 kmol/hr
0.00263 kJ/hr
7.303E-07 kW

)
;5

;6

GAS OUTLET from top (STREAM 13)

Temperature=
Molar rate
Enthalpy

H2O (g)

Molar rate
5.50
Mass rate
98.99
Enthalpy 238100.31
66.14

Cl2 (g)

Molar rate
Enthalpy

17.82 kmol/h
0.02 kJ/hr
4.219E-06 kW

N2(g)

Molar rate
Enthalpy

47.40 kmol/h
0.03 kJ/hr
9.576E-06 kW

O2(g)

Molar rate
Enthalpy

2.22 kmol/h
1.639E-03 kJ/hr
4.552E-07 kW

14.34 kmol/h
0.01 kJ/hr
2.897E-06 kW
kmol/h
kg/h
kJ/hr
kW

;6

Temperature=
HCl(l)

Mass rate
Enthalpy

H2O (l)

Molar rate
Enthalpy

;6

;5

;7

LIQ OUTLET from bottom (STREAM 8)

50 C

HCl(g)

;5

45 C
2272.13 kg/h
118150.50 kJ/hr
32.82 kW
149.70 kmol/h
2.257E-01 kJ/hr
6.271E-05 kW

;6

;7

This is the amount of heat needed to be removed from the HCl absorber.

COOLER AFTER MIXER AT RECYCLE STREAM

(STREAM 9)
(STREAM 10)
RECYCLE BACK TO SCRUBBER
ACID FRESH FEED BEFORE RECYCLE
Temperature=

HCl(l)

Mass rate
Enthalpy

H2O
(l)

6
7

Molar rate
Enthalpy

45 C

Temperature=

1363.28 kg/h
70890.30 kJ/hr
19.69 kW

89.82 kmol/h H2O (l)

1.354E-01 kJ/hr
3.762E-05 kW

;5

)
(

HCl(l)

;6

)
6

7
1

This is the amount of heat needed to be removed by cooler.

Mass rate
Enthalpy

Molar rate
Enthalpy

20 C
14.81 kg/hr
370.32 kJ/hr
0.10287 kW

46.41 kmol/h
-0.01750 kJ/hr
-4.86E-06 kW

5.2.3 Stripping Column

The Cp value is calculated from thermodynamic heat capacity at different temperature
Overall heat balance equation :

Q = the heat supplied or released

By referring to the Cp table that we have constructed at different temperature,

The enthalpy in each stream =
Boiling point of 22wt% HCL(aq) = 104.4C, Cp= 2.912kJ/kg.K=106.288kJ/kmol.K
Boiling point of 36wt% HCL(aq) = 61C, Cp= 2.46kJ/kg.K=89.79kJ/kmol.K
39wt% HCL(aq) Cp= 2.44kJ/kg.K=89.06kJ/kmol.K

Constant values for calculation of specific heat capacities (Table B2)

, ( )

A
B
C
D

HCl (g)
2.91E-02
-1.34E-06
9.72E-09
-4.34E-12

H2O (l)
7.540E-02

H2O (g)
3.346E-02
6.880E-06
7.604E-09
-3.593E-12

Calculation of specific enthalpy at different temperature:

Sample calculation for Mixer:

Cl2 (g)
3.360E-02
1.367E-05
-1.607E-08
6.473E-12

Stream 15
45

20

45

25

,2

Stream 23
53 5

20

53 5

20

53 5

,2

20

,2

Stream 3

Assume it is adiabatic operation, the temperature of mixed outlet stream is calculated.

,
20

,2
20

,2
20

MIXER 3
(STREAM 15)
IN FROM SPLITTER
Temperature =

(STREAM 23)
IN FROM RECYCLE (36%HCl)

45C

Total molar rate=

85

Total mass rate=

1987

kmol/h
kg/h
Cl2 (g)

HCl(aq)

H2O (l)

Molar rate
Mass rate
Mole frac
Molar rate
Mass rate

25
909
0.2937
60
1078

kmol/h
kg/h

HCl(aq)

kmol/h
kg/h

H2O (l)

Temperature =

53.5C

Total molar rate=

169

kmol/h

Total mass rate=

3741

kg/h

Molar rate
Mass rate
Mole frac
Molar rate
Mass rate
Mole frac
Molar rate
Mass rate

0.1897
13
0.0011
37
1354
0.2192
132
2374

kmol/h
kg/h
kmol/h
kg/h
kmol/h
kg/h

Mole frac

0.7063

Mole frac

Qin= 2877786 kJ/h

Qin = 11279538kJ/hr

Heat of mixing= 55064.64 kJ/h

(STREAM 16)
MIXER OUTLET
Temperature =
Total molar rate=
Total mass rate=
Cl2 (g)

HCl(aq)

H2O (l)

Molar rate
Mass rate
Mole frac
Molar rate
Mass rate
Mole frac
Molar rate
Mass rate
Mole frac

Q= 14212359 kJ/h

49.00 C
254 kmol/h
5728 kg/h
0.1897
13
0.0007
62
2262
0.2441
192
3452
0.7552

kmol/h
kg/h
kmol/h
kg/h
kmol/h
kg/h

0.7797

EXPELLER
(STREAM 16)
LIQUID FEED
Total molar rate=
Total mass rate=
Cl2 (g)

HCl(aq)

H2O (l)

Qin=

(STREAM 14)
STEAM IN
254 kmol/h
5728 kg/h

Molar rate
Mass rate
Mole frac
Molar rate
Mass rate

0.1897
13
0.0007
62
2262

kmol/h
kg/h

Mole frac

0.2441

Molar rate
Mass rate
Mole frac

192 kmol/h
3452 kg/h
0.7552

kmol/h
kg/h

Total molar rate=

Total mass rate=

Steam at 200psig
From steam table:
Temp of Sat. Steam
Latent Heat of Steam
Specific Enthalpy of Sat.
Steam
Specific Enthalpy of Sat.
Water

12326352 kJ/h

Qin=

(STREAM 19)
OUT, LIQUID( EFFLUENT)
Temperature =
Total molar rate=
Total mass rate=

Molar rate
Mass rate

Temperature =

44.45 C
218 kmol/h
4409 kg/h

27 kmol/h
970 kg/h

198 C
1949 kJ/kg
2791

kJ/kg

842

kJ/kg

15527846 kJ/h

STREAM 17
OUT, VAPOR ( RECYCLE)

Total molar rate=

Total mass rate=
Cl2 (g)

HCl(aq)

19 kmol/h
335 kg/h

HCl(g)

Molar rate
Mass rate
Mole frac
Molar rate
Mass rate

120C
51 kmol/h
1589 kg/h
0.1858
13
0.0036
35
1293

kmol/h
kg/h
kmol/h
kg/h

Mole frac
Molar rate
Mass rate
Mole frac

H2O (l)

Qout=

0.1221
191 kmol/h
3439 kg/h
0.8779

8873176 kJ/h

Mole frac
Molar rate
Mass rate
Mole frac

H2O (g)

Qout=

0.6899
16 kmol/h
283 kg/h
0.3065

18981023 kJ/h

COOLER CONDENSER
(STREAM 17)
VAPOR IN
Temperature = 120C
Total molar rate=
Total mass rate=
Cl2 (g)

HCl(g)

H2O (g)

Qin=

Molar rate
Mass rate
Mole frac
Molar rate
Mass rate
Mole frac
Molar rate
Mass rate
Mole frac

55 kmol/h
1654 kg/h
0.1858
13
0.0034
35
1293
0.6446
19
348
0.3521

kmol/h
kg/h
kmol/h
kg/h
kmol/h
kg/h

16939830 kJ/h

Stream 18
water out
Temperature =
Total molar rate=
Total mass rate=

Stream 4
Out, vapor ( recycle)
80C
19 kmol/h
335 kg/h

Temperature =

80.0C

Total molar rate=

Total mass rate=
Cl2 (g)
Molar rate
Mass rate
Mole frac
HCl(g)
Molar rate
Mass rate

36
1319
0.1858
13
0.0051
35
1292.6494

kmol/h
kg/h
kmol/h
kg/h
kmol/h
kg/h

Mole frac
Molar rate
Mass rate
Mole frac

H2O (g)

Qout=
4646435 kJ/h
Qout=
Total heat removed by the system = 8472533 kJ/h

0.9747
1 kmol/h
13 kg/h
0.0202

3820862 kJ/h

Cooling water at 13C is supply at 50 m3/h

The temperature of water will being heated up to 40.54 C
Cooler 3
Stream 19
Temperature =
44.45C
Total molar rate=
Total mass rate=
HCl(aq)

H2O (l)

Qin=

Molar rate
Mass rate
Mole frac
Molar rate
Mass rate
Mole frac
8874307 kJ/h

Stream 20
Temperature =
35.0C

218 kmol/h
4409 kg/h
27
970
0.1221
191
3439
0.8779

Total molar rate=

Total mass rate=

kmol/h
kg/h

HCl(aq)

kmol/h
kg/h

H2O (l)

Qout=

Molar rate
Mass rate
Mole frac
Molar rate
Mass rate
Mole frac
3283563 kJ/h

Total heat removed by the system = 5590744 kJ/h

Cooling water at 13C is supply at 35 m3/h
The temperature of water will being heated up to 38.21 C

218 kmol/h
4409 kg/h
27
970
0.1221
191
3439
0.8779

kmol/h
kg/h
kmol/h
kg/h

5.2.4 2nd stage HCl Absorber

Assumption:
It is assumed that the packed column scrubber is ADIABATIC.
Energy Balance:

At inlet:

HCL Absorber
STREAM 13 (From Scrubber)
Temperature=

HCl(g)

H2O (g)

Cl2 (g)

N2(g)

Mass rate
Enthalpy

STREAM 20(From Cooler 2)

50 C
522.70 kg/h
74356.73 kJ/hr
21 kW

HCl(l)

Molar rate
Enthalpy

5500.00 mol/hr H2O (l)

4637.72 kJ/hr

Molar rate
Enthalpy

1.288
17820.00
15186.90
4.22

kW

mol/hr
kJ/hr
kW

Molar rate 47400.00 mol/hr

Enthalpy 34472.41 kJ/hr
9.58 kW

O2(g)

Temperature=

Molar rate
Enthalpy

2220.00 mol/hr
1638.66 kJ/hr
0.46 kW

Molar rate
Enthalpy

35 C

26573.60 mol/hr
19328.06 kJ/hr
5.37 kW

Molar rate 191064.10 mol/hr

Enthalpy 360155.83 kJ/hr
100.04 kW

Q1in = 36.19 kW

Q2in = 105.41 kW

At outlet:
(STREAM 24)
TO DRYER
Temperature=

(STREAM 21)
TO SPLITTER2
53.5 C

Temperature=
Molar rate
Enthlpy

HCl(g)

Molar rate
Enthalpy

1.71 mol/hr Cl2(g)

1.64 kJ/hr
0.00 kW

H2O (g)

Molar rate
Enthalpy

50000.00 mol/hr HCl(l)

55702.36 kJ/hr

Mass rate
Enthalpy

15.47 kW
Cl2 (g)

Molar rate
Enthalpy

17613.60 mol/hr
H2O (l)
604.85 kJ/hr
0.17 kW

N2(g)

Molar rate
Enthalpy

47400.00 mol/hr
45520.40 kJ/hr
12.64 kW

O2(g)

Molar rate
Enthalpy

2220.00 mol/hr
66.05 kJ/hr
0.02 kW

Q3out = 28.3 kW

53.5 C
206.40 mol/hr
7.09 kJ/hr
1.97E-03 kW
1490.44 kg/h
218191.53 kJ/hr
60.61 kW

Molar rate 146558.40 mol/hr

Enthalpy
11050.50 kJ/hr
3.070 kW

Q4out = 63.68 kW

Some energy is also generated by heat of solution of HCl(g) into H2O(l):

Heat of solution of HCl(g) into H2O(l)= 75.1 kJ/mol

Number of moles of HCl(g) being absorbed = 14338.288 mol/hr

Enthalpy (Heat of solution) = Number of mole/hr x heat of solution/mol

= 14338.288 mol/hr x 75.1 kJ/mol
= 1076805 kJ/hr = 299.1126 kJ/s

Energy Balance
Energy in + Energy generated -Energy Out -Energy Consumption = Energy Accumulated

Assumption:

No eenergy consumption and energy accumulated = 0

Energy Out = Energy in + Energy generated

Energy in = Inlet Enthalpy
= Q1in + Q2 in
= 36.19kW + 105.41kW
= 141.6 kW
Energy out = Outlet Enthalpy = Q3 + Q4 + Q5 (Heat gained by irrigating liquor)
= 28.30 + 68.78 kW
= 91.98 kW + Q5

Energy generated = Heat of solution

= 299.1126 kW
Q5 = m Cp dT
91.98kW + Q5 = 141.6kW + 299.1126kW
Q5 = 348.73 kW
Q5 = Heat gained by irrigating liquor
Q5 = m Cp dT

(
(
)

)(
)

1255437.36kJ = 44139.09415* (T-298)

T(outlet) = 326.5 K
= 53.5 C (to dryer and splitter)

)(

)
(

At Splitter 2 inlet:
(STREAM 21)
FROM ABSORBER
Temperature =

53.5C

Total molar rate=

Total mass rate=

187.65 kmol/h
9097.21 kg/h

Cl2 (g)

Molar rate
Mass rate
Mole frac

0.21 kmol/h
14.65 kg/h
0.0011

7.077E+00 kJ/h

HCl(l)

Molar rate
Mass rate
Mole frac

40.89 kmol/h
1490.44 kg/h
0.2179

6.367E+04 kJ/h

H2O (l)

Molar rate
Mass rate
Mole frac

146.56 kmol/h
2638.05 kg/h
0.7810

5.912E+05 kJ/h

O2 (g)

Molar rate
Mass rate
Mole frac

0.00 kmol/h
0.00 kg/h
0.00

N2 (g)

Molar rate
Mass rate
Mole frac

0.00 kmol/h
0.00 kg/h
0.00

Enthalpy

At Splitter 2 outlet:
(STREAM 23)
OUTLET TO EXPELLER

(STREAM 22)
OUTLET EFFLUENT

Temperature = 53.5C

Temperature = 53.5C

Total molar rate=

Total mass rate=
Cl2 (g)

HCl(l)

H2O (l)

O2

N2

Molar rate
Mass rate
Mole frac
Molar rate
Mass rate
Mole frac
Molar rate
Mass rate
Mole frac
Molar rate
Mass rate
Mole frac
Molar rate
Mass rate
Mole frac

168.89 kmol/h
3623.70 kg/h
0.1858
13.18
0.0011
36.80
1341.40
0.2179
131.90
2374.25
0.7810
0.00
0.00
0.00
0.00
0.00
0.00

Total molar rate=

Total mass rate=

kmol/h
kg/h

Cl2 (g)

kmol/h
kg/h

HCl(l)

kmol/h
kg/h

H2O (l)

kmol/h
kg/h

O2

kmol/h
kg/h

N2

Molar rate
Mass rate
Mole frac
Molar rate
Mass rate
Mole frac
Molar rate
Mass rate
Mole frac
Molar rate
Mass rate
Mole frac
Molar rate
Mass rate
Mole frac

18.77 kmol/h
5435.55 kg/h
0.0206
1.4646
0.0011
4.09
149.04
0.2179
14.66
263.81
0.7810
0.00
0.00
0.00
0.00
0.00
0.00

Qout = Outlet Enthalpy = Enthalpy of Stream 22 + Stream 23

Enthalpy of Stream 23 = 5.894E+05 kJ/hr
Enthalpy of Stream 22 = 6.549E+04 kJ/hr

Change in Energy,

= Qin Qout
= Enthalpy at Stream 21 - (Enthalpy at Stream 22 and Stream 23)

kmol/h
kg/h
kmol/h
kg/h
kmol/h
kg/h
kmol/h
kg/h
kmol/h
kg/h

= 654890 ((589400+65490) kJ/h

= 0 kJ/h
Splitter 2 is an adiabatic splitter.

5.2.5 Dryer
At cooler:
COOLER

IN

OUT(TO DRYER)

Total mass rate=

Total mole rate=

3558.97 kg/hr
117.37 kmol/hr

Total mass rate=

Total mole rate=

3558.97 kg/hr
117.69 kmol/hr

H2O

Mass rate =
Mole rate=
Mole fraction=

900.00 kg/hr
50.00 kmol/hr
0.43

H2O

Mass rate =
Mole rate=
Mole fraction=

900.00 kg/hr
50.00 kmol/hr
0.42

Cl2

Mass rate =
Mole rate=
Mole fraction=

1260.87 kg/hr
17.76 kmol/hr
0.15

Cl2

Mass rate =
Mole rate=
Mole fraction=

1260.87 kg/hr
17.76 kmol/hr
0.15

HCl

Mass rate =
Mole rate=
Mole fraction=

0.06 kg/hr
0.00 kmol/hr
0.00

HCl

Mass rate =
Mole rate=
Mole fraction=

0.06 kg/hr
0.00 kmol/hr
0.00

O2

Mass rate =
Mole rate=
Mole fraction=

71.04 kg/hr
2.22 kmol/hr
0.02

O2

Mass rate =
Mole rate=
Mole fraction=

71.04 kg/hr
2.54 kmol/hr
0.02

N2

Mass rate =
Mole rate=
Mole fraction=

1326.99 kg/hr
47.39 kmol/hr
0.40

N2

Mass rate =
Mole rate=
Mole fraction=

1326.99 kg/hr
47.39 kmol/hr
0.40

Total Enthalpy In= 198930.10 kJ/hr

Total Enthalpy Out = 104112.95 J/hr

Change in Enthalpy= 94817.15 kJ/hr

Chill water can range from (2 to 7 C) while cooling water can range from (13 to 25 C).
Both can be used for cooling.
CHILLING WATER
INLET

Outlet

13.00 Deg C
707.36 kg/hr
39.30 kmol/hr

Mass of water=
Mole=
Enthalpy =

980.20 kJ/kmol
38519.47 kJ/hr

45.00 Deg C
707.36 kg/hr
39.30 kmol/hr

Mass of water=
Mole=
Enthalpy =

3393.00 kJ/kmol
133336.62 kJ/hr

Change in enthalpy = 94817.15 kJ/hr

Change in energy= 0.00kJ/hr
(Adiabatic Heat Exchanger)

Temperature of aqueous sulfuric acid:

Enter = 20 Deg C

Temp Ref= 0.00 Deg C

Exit = 96.99 Deg C

Specific heat capacity of aqueous sulfuric acid (Sulfuric acid(aq),T : 5 to 300 K)

wt%
98.00
70.00
40.00
30.00
15.00

Specific Heat Capacity

cal/g.K
kJ/kg.K
kJ/kmol.K
0.33
1.37
0.01
0.47
1.98
0.02
0.68
2.84
0.03
0.77
3.23
0.03
0.88
3.67
0.04

Source: http://pubs.acs.org/doi/pdf/10.1021/ja01486a014
Specific heat capacity of water in 98% sulfuric acid outlet (kJ/kmol) = 1508.00kJ/kmol
Specific heat capacity of water in 30% sulfuric acid outlet (kJ/kmol) = 7313.30kJ/kmol
Heat of Dilution due to Sulfuric acid(98% to 70%) = -65.00 Btu/lb = -151.19 kJ/kg

At 1st Dryer:
Temperature of aqueous sulfuric acid
Inlet = 20 oC

Tref = 0 oC

Outlet = 95 oC

Using the same specific heat capacity earlier, heat of dilution is calculated:

Specific heat capacity of water in 98% H2SO4 acid outlet (kJ/kmol) = 1508.00 kJ/kmol
Specific heat capacity of water in 30% H2SO4 acid outlet (kJ/kmol) = 7142.41 kJ/kmol
Heat of Dilution due to H2SO4 (70% to 30%) = -340 Btu/lb = -790.84 kJ/kg

ENERGY BALANCE IN FIRST DRYER

INLET
OUTLET
SULFURIC ACID 70% , 20 C
SULFURIC ACID 30%
Total mass=
Total mole=

555.86 kg/hr
13.23 kmol/hr

Total mass=
Total mole=

1297.00 kg/hr
54.41 kmol/hr

Mass H2SO4=
Mole=
Mole fraction=

389.10 kg/hr
3.97 kmol/hr
0.30

Mass H2SO4=
Mole=
Mole fraction=

389.10 kg/hr
3.97 kmol/hr
0.07

Mass H20=
Mole=
Mole fraction=

166.76 kg/hr
9.26 kmol/hr
0.70

Mass H20=
Mole=
Mole fraction=

907.90 kg/hr
50.44 kmol/hr
0.93

Total Enthalpy=

13972.15 kJ/hr

STREAM, 28 DEG C

Total Enthalpy=

52551.78 kJ/hr

STREAM,28 DEG C

Total mass=
Total mole=

3558.97 kg/hr
117.69 kmol/hr

Total mass=
Total mole=

2817.82 kg/hr
76.52 kmol/hr

Mass of water=
Mole=
Mole fraction=

900.00 kg/hr
50.00 kmol/hr
0.42

Mass of water=
Mole=
Mole fraction=

158.86 kg/hr
8.83 kmol/hr
0.12

Mass of Cl2=
Mole=
Mole fraction=

1260.87 kg/hr
17.76 kmol/hr
0.15

Mass of Cl2=
Mole=
Mole fraction=

1260.87 kg/hr
17.76 kmol/hr
0.23

Mass of HCl=

0.06 kg/hr

Mass of HCl=

0.06 kg/hr

Mole=
Mole fraction=

0.00 kmol/hr
0.00

Mole=
Mole fraction=

0.00 kmol/hr
0.00

Mass of O2=
Mole=
Mole fraction=

71.04 kg/hr
2.54 kmol/hr
0.02

Mass of O2=
Mole=
Mole fraction=

71.04 kg/hr
2.54 kmol/hr
0.03

Mass of N2=
Mole=
Mole fraction=

1326.99 kg/hr
47.39 kmol/hr
0.40

Mass of N2=
Mole=
Mole fraction=

1326.99 kg/hr
47.39 kmol/hr
0.62

Enthalpy=

104112.95 kJ/hr

Total Enthalpy Inlet =118085.10 kJ/hr

Enthalpy=

65533.32 kJ/hr

Total Enthalpy Outlet =118085.10 kJ/hr

Change of Enthalpy= 0.00kJ/hr

Intercooler Heat duty = 360265.01 kJ/hr

At 2nd Dryer:
ENERGY BALANCE IN 2ND DRYER
INLET
OUTLET
SULFURIC ACID 98% , 20 C

SULFURIC ACID 70%

Total mass=
Total mole=

397.04 kg/hr
4.41 kmol/hr

Total mass=
Total mole=

555.86 kg/hr
13.23 kmol/hr

Mass H2SO4=
Mole=
Mole fraction=

389.10 kg/hr
3.97 kmol/hr
0.90

Mass H2SO4=
Mole=
Mole fraction=

389.10 kg/hr
3.97 kmol/hr
0.30

Mass H20=
Mole=
Mole fraction=

7.94 kg/hr
0.44 kmol/hr
0.10

Mass H20=
Mole=
Mole fraction=

166.76 kg/hr
9.26 kmol/hr
0.70

Total Enthalpy=

666.37 kJ/hr

Total Enthalpy=

STREAM, 28 C

8933.43 kJ/hr

STREAM,28 C

Total mass=
Total mole=

2817.82 kg/hr
76.52 kmol/hr

Total mass=
Total mole=

2659.01 kg/hr
67.69 kmol/hr

Mass of water=
Mole=
Mole fraction=

158.86 kg/hr
8.83 kmol/hr
0.12

Mass of water=
Mole=
Mole fraction=

0.04 kg/hr
0.00 kmol/hr
0.00

Mass of Cl2=
Mole=
Mole fraction=

1260.87 kg/hr
17.76 kmol/hr
0.23

Mass of Cl2=
Mole=
Mole fraction=

1260.87 kg/hr
17.76 kmol/hr
0.26

Mass of HCl=
Mole=
Mole fraction=

0.06 kg/hr
0.00 kmol/hr
0.00

Mass of HCl=
Mole=
Mole fraction=

0.06 kg/hr
0.00 kmol/hr
0.00

Mass of O2=
Mole=
Mole fraction=

71.04 kg/hr
2.54 kmol/hr
0.03

Mass of O2=
Mole=
Mole fraction=

71.04 kg/hr
2.54 kmol/hr
0.04

Mass of N2=
Mole=
Mole fraction=

1326.99 kg/hr
47.39 kmol/hr
0.62

Mass of N2=
Mole=
Mole fraction=

1326.99 kg/hr
47.39 kmol/hr
0.70

Enthalpy=

65533.32 kJ/hr

Total Enthalpy In = 66199.69 kJ/hr

Change of Enthalpy= 0.00 kJ/hr
This is an abiabatic dryer.

Enthalpy=

57266.25 kJ/hr

Total Enthalpy Out = 66199.69 kJ/hr

Intercooler Heat duty = 67759.86 kJ/hr

At Liquefaction Section:
Liquid Chlorine
Boiling point of Chlorine =

-31.50 C

From Phase Diagram=

Pressure=

-20.00 C
2.00 bar

LIQUEFACTION/COMPRESSOR
INLET
FROM DRYER (28 C)

OUTLET
CHLORINE STORAGE(-20 C)

Total mass=
Total mole=

2659.01 kg/hr
67.69 kmol/hr

Total mass=
Total mole=

1261.00 kg/hr
17.76 kmol/hr

Mass of water=
Mole=
Mole fraction=

0.04 kg/hr
0.00 kmol/hr
0.00

Mass of water=
Mole=
Mole fraction=

0.00 kg/hr
0.00 kmol/hr
0.00

Mass of Cl2=
Mole=
Mole fraction=

1260.87 kg/hr
17.76 kmol/hr
0.26

Mass of Cl2=
Mole=
Mole fraction=

1260.87 kg/hr
17.76 kmol/hr
1.00

Mass of HCl=
Mole=
Mole fraction=

0.06 kg/hr
0.00 kmol/hr
0.00

Mass of HCl=
Mole=
Mole fraction=

0.05 kg/hr
0.00 kmol/hr
0.00

Mass of O2=
Mole=
Mole fraction=

71.04 kg/hr
2.54 kmol/hr
0.04

Mass of O2=
Mole=
Mole fraction=

0.00 kg/hr
0.00 kmol/hr
0.00

Mass of N2=
Mole=
Mole fraction=

1326.99 kg/hr
47.39 kmol/hr
0.70

Mass of N2=
Mole=
Mole fraction=

0.07 kg/hr
0.00 kmol/hr
0.00

Enthalpy=

57266.25 kJ/hr

Sniff Gas (28 Deg C)

Total mass=
1398.01 kg/hr
Total mole=
49.93 kmol/hr

Enthalpy=

-11938.59 kJ/hr

Mass of water=
Mole=
Mole fraction=

0.04 kg/hr
0.00 kmol/hr
0.00

Mass of Cl2=
Mole=
Mole fraction=

0.00 kg/hr
0.00 kmol/hr
0.00

Mass of HCl=
Mole=
Mole fraction=

0.01 kg/hr
0.00 kmol/hr
0.00

Mass of O2=
Mole=
Mole fraction=

71.04 kg/hr
2.54 kmol/hr
0.05

Mass of N2=
Mole=
Mole fraction=

1326.92 kg/hr
47.39 kmol/hr
0.95

Enthalpy=

16714.03 kJ/hr

Total Change in Enthalpy= 52490.82 kJ/hr

R-404A Refrigerant
Component
CHF2CF3
CH3CF3
CH2FCF3

a
11.70
1.37
4.64

b
0.02
0.08
0.06

c
0.00
0.00
0.00

d
0.00
0.00
0.00

composition
0.44
0.52
0.04

Tref = 0 OC
Specific enthalpy, H (kJ/kmol)
T(Deg C) CHF2CF3
CH3CF3
CH2FCF3
-40.00
-468.49
-56.41
-186.71
-20.00
-234.25
-28.21
-93.35
-5.00
-58.56
-7.05
-23.34
INLET(-40 C)
OUTLET(-5 C)
Total Mole=
243.75 kmol/hr
Total Mole=
243.75 kmol/hr
CHF2CF3
107.25 kmol/hr
CHF2CF3
107.25 kmol/hr
CH3CF3
126.75 kmol/hr
CH3CF3
55.77 kmol/hr

CH2FCF3
Enthalpy=

9.75 kmol/hr

CH2FCF3

-59216.90 kJ/hr

Enthalpy=

2.23 kmol/hr
-6726.08 kJ/hr

Change in Enthalpy = 52490.82 kJ/hr

Net Change of Enthalpy within Compressor= 0.00kJ/hr
Adiabatic Compressor

Minimum Power requirement for the compressor

2

;5

3
2

6.0 UNIT OPERATION DESIGN

6.1 Fluidized Bed Reactor

Particle Size, (m)

0 - 50

% wt/wt
0

average size, dv (m)

25

50 -100
100 -150
150 - 200
200 -250
250 - 300
300 - 350
>350

0.39
14.61
43
27
11.6
3.26
0.14

75
125
175
225
275
325

Bulk density at minimum fluidization = 288 kg/m3

Density of catalyst,

= 640 kg/m3

0.55

Superficial velocity = 0.2 m/s (assumed)

Particle shape factor,

= 0.7

Residence time in reactor = 25s

;3

Diameter of sphere having same volume as average particle:

(

Reactants molar flow rate = 133.7 kmol/h

Operating temperature = 623 K
Reactants volumetric flow rate,

Diameter of the fluidized bed reactor, D

2)

Density of reactant gases,

Calculating the gas flow rate at minimum fluidization using Ergun equation,
(
3

(
2

)
3

)
3

Minimum fluidization velocity,

Height of unexpanded bed, H

)
2

Void fraction of the unexpanded bed = 0.5

(

Terminal velocity,
(

)(

)2 (

Expansion ratio, R

Expanded bed height,

The corresponding fluidized bed voidage,

(

Pressure drop across the bed,

)(

6.1.1 GAS DISTRIBUTOR PLATE

The pressure drop across the distributor plate,

pressure drop across the bed)
Area of holes,

(23% of the

)2

Number of holes, N
Diameter of holes, d = 6mm

Cross sectional area of reactor, A = 9.46

Arranging the holes on a triangular pitch to get a uniform distribution of total hole
area
)0 5

6.1.2 CYCLONE DESIGN

2

K- Proportionality factor = 0.9

Q- inlet gas flow rate to cyclone
P- absolute pressure
T temperature
= 1177 Pa
Stairmand High Efficiency Cyclone is used to design cyclone for this process.
Euler Number, Eu = 320, Stokes Number,
size range
( m)
G(x)

50100
0.39

100150
15.00

150200
58.00

;4

50

200250
85.00

250300
96.60

300350
99.86

G(x)

Grade Efficiency Curve

100
90
80
70
60
50
40
30
20
10
0

50

50

100

150

200

250

300

Particle size, (m)

Characteristic velocity,

Eu = Euler Number

pressure drop, Pa
density of gas inlet
characteristic velocity
Reactor product flow rate, (cyclone volumetric flow inlet)

Diameter of Cyclone, D

Checking cut size value,

50

350

50

50

50

The calculated cut size value is almost the same with the cut size value obtained from
the grade efficiency graph

Actual length (m)

A
3.28

B
2.05

C
1.23

E
0.31

J
0.41

L
0.16

K
0.41

N
0.41

6.2 1st stage HCl Absorber

6.2.1 Type of Packing

Ceramic Intalox Saddle is chosen because:

Resist corrosion by HCl acid

Diameter=
Bulk density=
Surface area=
Packing factor, Fp=
Corresponding column
diameter
Suitable packing height range=
Pressure drop, P >=

38
62.5
194
170
0.3-0.9
0.5-0.75
15-50

6.2.2 Calculation of Column Diameter

Mass flow rate of inlet gas, G=
Mass flow rate inlet liquid solvent,
L=
Gas temperature, TG=
Liquid solvent temperature, TL=
Pressure of inlet gas,P=

mm
kg/m3
m2/m3
m-1
m
m
mmH20/mm

4386.76 kg/h
3250.18
338
293
1

kg/h
K
K
atm

Abscissa of Fig 11.44

(Sinnott, R.K. Coulson & Richardson's Chemical Engineering Design, Vol 6. ):
Pressure drop, P=
Liq inlet density, L=
Gas inlet density, G=
Viscosity of liq inlet, L=

42
1179
1.1528
0.0018

mmH20/m packing
kg/m3
<---HCl 36 wt%, T =20 C
kg/m3
<---HCl gas, T=65 C
Pa.s

Using the generalise pressure drop correlation above at P=42, we get:

K4= 1.6
Using Eqn 11.118 (pg 604, Coulson & Richardson's Chemical Engineering Design):

1
2

4 (

1 2

01

;3 0 1

Note: Vw = gas mass flow rate per unit column cross-sectional area, kg/m2.s
Cross-sectional area of column:

Diameter of column:

A larger size packing may be considered.

6.2.3 Equilibrium data for HCl(g) dissolving in HCl acid

To get the equilibrium curve:

Mass flux of entering gas, Gm=

Mass flux of entering liquid, Lm=
Gm/Lm =

(
1

2 )

7975.93 kg/h
5909.42 kg/h
1.35

The resulting equilibrium line:

)2

Operating line
Top (2)
Bottom (1)

Liquid,x
0.157
0.523

Slope of operating line=

Gas, y
0.354
0.800

1.2186

Mol frac of HCl in gas, y

Equilibrium curve of HCl acid

0.900
0.800
0.700
0.600
0.500
0.400
0.300
0.200
0.100
0.000

y = 1.2186x + 0.1627

y = 1.35x

Operating
Linear (Equilibrium)
Linear (Operating)
0

0.2

0.4

0.6

Mol frac of HCl in liquid, x

y1/y2
mGm/Lm

Equilibrium

2.26
1.6

0.8

Based on Fig 11.4 above

(Sinnott, R.K. Coulson & Richardson's Chemical Engineering Design, Vol 6. ):
Nog =2

6.2.4 Height of Transfer Unit

Equation for the effective area, aw

0 75

01

;0 05

Equation to find mass coefficient kL:

2 3

1 3

07

;0 5

1 3

04

( )

;2 0

( )

02

where K5=
Lw*=
Vw*=
aw=
a=
dp=
c=

L=
kG=
kL=
R=

5.23 for packing sizes above 15 mm

and 2.00 for sizes below 15mm
liquid mass flow rate per unit crosssectional area, kg/m2.s
gas mass flow rate per unit cross-sectional area, kg/m2.s
effective interfacial area of packing per unit volume, m2/m3
actual area of packing per unit volume (Table 11.3), m2/m3
packing size, m
criticial surface tension for the particular packing material given below:
c,
Material
mN/m
Ceramic
61
Metal (steel)
75
Plastic (Polythylene)
33
Carbon
56
liquid surface tension, N/m
gas film mass transfer coefficient, kmol/m2.s.atm or kmol/m2.s.bar
liquid film mass transfer coefficient, kmol/m2.s (kmol/m3) = m/s
0.08206 atm m3/kmol K or 0.08314 bar m3/kmol K

The film transfer unit heights, HTU, are given by:

where P=
Ct=
GM=
LM=

column operating pressure, atm or bar

total concentration, kmol/m3 = L / Mw of solvent
molar gas flow rate per unit cross-sectional area, kmol/m2.s
molar liquid flow rate per unit cross-sectional area, kmol/m2.s

To find aw:
a=
194 m2/m3
c=
61 mN/m
L=
69 mN/m
v= 0.00001348 Pa.s
L=
0.00199 Pa.s
L=
1179 kg/m3
g=
9.81 m/s2
dp=
38 mm
Vw*=
2.2155 kg/m2.s
Lw*=
1.9345 kg/m2.s
01

0 75

;3

;3

02

;0 05

aw=

578.03

DL
Dv first.
To find kL and kgmust
find
and

;5

)(

To find DV:
Using Chapman-Enskog kinetic theory for gases:

Since inlet gas has five components, calculation for DV is based on multi-component mixtures.
So, we need to use Wilki approximation:

Lennard-Jones constants:

H2O
HCl
Cl2
N2
O2

T at gas inlet:
Interaction
1_2
1_3
1_4
1_5

Mw
(g/mol)
18
36.5
35.5
28
32

i
1
2
3
4
5

, (A)
2.649
3.305
4.115
3.681
3.433

/K (K)
y (gas inlet)
356
0.1514
360
0.3101
357
0.1423
91.5
0.3785
113
0.0177

338 K
1-i
8.862529
11.43792
10.01723
9.247681

AB/K
T/(AB/K)
357.99
0.94
356.50
0.95
180.48
1.87
200.57
1.69

AB
1.484
1.476
1.099
1.141

D1-i
1.029E-06
6.239E-07
1.141E-06
1.257E-06

*Source of Lennard-Jones Constants : WWWR, Table K1 & K2, pg 694-695

;2
;2

;2

;2

;2

To find DL:
DL (H2O-HCl at T=25C) = 3.10E-05 cm2/s
*Source: Perry's Chemical Engineering Handbook (pg -259)
Since the value is given at 25 C, we need to extrapolate the value to the stream
temperature.

yi'
0.37
0.17
0.45
0.02

;5

<55
;5

;9

Substitute all values into equation to get Kl & kG:

1 3

2 3

;0 5

;4

)0 4

;9

)
;6
07
;5

1 3

;5

;6 )

);2 0
;5
2

By using inlet gas flow rate & inlet liq flow and area of column, we get:
Gm
0.0633 kmol/m2.s
Lm
0.0879 kmol/m2.s
Substitute all values into the equations of HG and HL:

;5

6.3 Stripping Column

This stripping column is known as a steam stripping column because it utilized steam as
a stripping agent. It consists of one liquid inlet, one gas inlet stream with one liquid
outlet, one gas outlet stream. The inlet liquid stream consist of HCL solution and very
trace amount of chlorine. Thus, it can be assume as pseudo-binary system. The objective
of this stripper is to strip the HCL gas out from the solution and recycle back to the
reactor to increase the recovery and efficiency of the plant.

The inlet stream consists of 2262kg/h of HCl, 3452kg/h of H2O and 0.0007kg/h of Cl2 is
fed at 322K to the column. The inlet steam consist of 335kg/h of saturated vapor which
fed at 470K . The steam works to heat up the liquid stream and strip out the HCl vapor
to the top of the column while the remaining solution been cool down and move to the
bottom of the column. The overall mass and energy balance have been shown in the
table presented before.
Given Data:
Liquid inlet temperature : 322K
Inlet steam temperature : 470K
Liquid outlet temperature : 317K
Vapor outlet temperature : 393K
Inlet liquid flow rate : 5728kg/h
Mass fraction : 0.6026 H2O, 0.3950 HCl, 0.0024 Cl2
Steam flow rate : 335kg/h
Outlet liquid flow rate : 4409kg/h
Mass fraction : 0.78 H2O, 0.22 HCl
Outlet vapor flow rate : 1589kg/h
Mass fraction : 0.1782 H2O, 0.8135 HCl, 0.0083 Cl2

6.3.1 Selecting type of column

Random Pack Column is chosen due to:
a) There is no serious pressure drop
b) Dealing with corrosive liquid where packed column will be cheaper.
c) The liquid holdup is lower in packed column.

d) Random pack column is relatively cheaper than structured pack column.

6.3.2 Choosing type of packing
Intalox Saddle Ceramic is chosen due to:
a) Large contact area per unit volume.
b) Provides higher flooding limit and low pressure drop.
c) Ceramic is chosen due to dealing with corrosive liquid.
d) 2 inch diameter is chosen with high packing factor and contact area per unit volume
6.3.3 Column Diameter Design
Liquid Flow Rate,L = 4409kg/h
Vapor Flow Rate, G = 1589kg/h
Density of liquid, L= 1041.8kg/m3
Density of vapor, V =(0.6899*36.5+0.3065*18.02+0.1858*71) /22.4
= 1.36kg/m3
Viscosity of liquid = 1.4377mPa.s
From table 22.1 MCcab & Smith 5th, packing factor for 2-inch ceramic intalox - saddles
=Fp=130, specific area of packing per unit volume,a =108m2/m3
From Sherwood Correlation,

For this stripper, we first assume the pressure drop to be 42mm water/m packing to
avoid flooding but smaller diameter to save cost.
( The standard for absorber and stripper will be 16-48mm water / m packing.)
( From topic 11.14.4, Coulson &Richardson)
From the graph, we can see that the corresponding K value is 1.4 while the
corresponding Kflooding value is 3.4

Then, we can calculate the G value from the K value obtained.

(From Coulson & Richardson volume-6)
(

0 1)

05

= 1.1708kg/m2.s

= 0.3770m2
(
= 0.69m

)0 5

Verify the diameter of the column with the diameter of the packing which is 0.0508m

The ratio is greater than 12, thus it is acceptable.

Thus, the diameter of the column is 0.69m.
6.3.4 Column Height Design
HETP method is utilized to calculate the height of this stripping column. The
equilibrium and operating line are plotted on the graph to determine the number of
HETP. The equilibrium line is obtained through the Henrys Law equation of HCL in
water because it is dilute solution.
( )
Henry Law Constant is relation with temperature where the correlation can be
determined by :
(

( )

T is the temperature of the liquid which is 317.65K.

PT = 1bar
Ho = 19
d(lnH)/d(1/T) = 9000
( )

1
)
298 15

From the graph, we can see there is 4 number of plate which is equivalent of HETP=4
The HETP value given for stripping column is 1.83m. ( By Henry Kister )
Height of packing = 1.83m*HETP
= 1.83m*4
= 7.32m
From the K value that we obtained from the Sherwood Correlation Graph, the
percentage of flooding can be estimated .

The flooding percentage is lower than 80% which mean the design is acceptable.

6.3.5 Calculation of operating velocity and flooding velocity

From the Sherwood correlation, we can obtain the equation below to compute the
velocity of the solution. (From Ludwig, pg-159)
(

)
(

)0 1

)0 5

When K=1.4

When KFlooding =3.4

6.3.6 Calculation of Pressure drop

(From McCabe & smith 5th edition)
07

07

= 3.62inch H2O/ ft
= 301.67mm H2O/m packing
Total pressure can be determined by the graph.
2

6.3.7 Calculation of wetting rate

;3

It is greater than the minimum wetting rates which is 0.07*10^-3m3/m2.s proposed by

Kister (1992)
6.3.8 Calculation of the number of liquid distribution stream of the top of the
packing
Number of liquid distribution at the top of the packing
( )2
)2

6.3.9 Design of liquid distributor and liquid redistributor

Spray type liquid distributor is chosen due to:
a) Low liquid rate
b) Cover large area of the tower
Liquid distributor is design to enable the uniform liquid distribution to achieve a higher
rate of mass transfer between the liquid and the gas.
Diameter of the nozzle estimated to be 5mm
;5

L-liquid volumetric flow rate(m^3/s)

A- area of nozzle(m^2)
n- number of nozzle
U-operating velocity(m/s)
;3
;5

Liquid distributor will locate at 0.2m above the packing

Liquid redistributor is designed to separate the single pack bed into two pack bed
beside collect the liquid at the wall and redistribute to the column.
Liquid redistributor will be located at the center of the packing which is 3.66m to
separate the packing into two zone.
Liquid redistributor also occupies 0.2m of the column.
Recommend vapor space at top = 0.5m
Recommend liquid space at bottom=0.7m
Total height of the column= 7.32+0.2+0.2+0.5+0.7
= 8.92m

6.3.10 Mechanical Design

Due to corrosive HCl and high temperature is involved in the process, the wall thickness
and material must be chosen which can withstand corrosion and heat beside have long
life span. Due to this factor, the thickness of the wall is designed to be 0.1m.
Thus, the total diameter of the column will be equal to
( )
The material that chooses to build the column is tantalum. This material is proved to be
suitable for stripping of HCl in the industry with its high resistant toward corrosive,
heat and pressure.
6.3.11 Design of P&ID
In order to control and maintain the operating condition and avoid run out of the unit
operation, a systematic process control and optimization system has been installed in
the stripping column. There are two main objective of the control process in the
stripping column:
1) To maintain the vapor outlet temperature by controlling the inlet steam flow rate.
2) To maintain the level of liquid in the stripping column by controlling the inlet liquid
flow rate.

Vapor outlet

Liquid inlet
TT

LC

LT

Steam inlet

Liquid outlet
Stripping Column

TC

Legend:

LT- Level detector

TT-Temperature sensor
LC-Level Controller
TC-Temperature Controller

There are two controllers in the unit operation to achieve the two objectives mentioned
above. Firstly, the temperature sensor which located at the vapor outlet will measure
the outlet vapor temperature. It would send the signal to the temperature controller
and any fluctuation from the optimum temperature will trigger the control valve at the
steam inlet to manipulate the flow rate of steam entering the stripping column.
Secondly, the level detector which attached with the stripping column will measure the
liquid level in the stripping column. When the level of the liquid exceed the optimum
level, it would send signal to the level controller and trigger the valve at the liquid inlet.
By controlling the flow rate of liquid inlet, the level of the stripping column can be
controlled.
6.3.12 Design Summary
Unit Operation : Random Packed Stripping Column
Function : To strip HCL gas from HCL solution
Operation : Continuous
Total pressure drop = 3018Pa/m
Percentage of flooding = 64%
HETP = 4

Diameter column = 0.69m

Wall Thickness = 0.10m
Total Diameter of Column = 0.89m
Height of packing = 7.32m
Liquid Distributor = 1 Spray type with 0.2m height
Liquid Redistributor = 1 with 0.2m height
Height of vapor space at top = 0.3m
Height of liquid space at bottom = 0.5m
Total Height of Column = 8.92m
Column Material = Tantalum
Packing type = Intalox Saddles
Packing Material = Ceramic
Packing size = 2inch /0.0508m
Packing arrangement = random

6.4 2nd stage HCl Absorber

One inlet liquid stream from the cooler which consists of hydrochloric acid, HCl(l), H 2O
with total molar flow rate of 217.64kmol/hr at the temperature of 35 0C flows to the
HCl absorber. Meanwhile, the other inlet gas stream with molar flow rate of
87.28kmol/hr which consists of Cl2,hydrogen chlroride-HCl(g) , H2O, N2 and O2 at
temperature of 50 0C which is from scrubber flows as another inlet stream. The two
liquid and gases inlet stream flow counter-currently and mass transfer occur between
the interface of the two stream. It is an absorption process in which HCl(l) in liquid will
absorb the HCl(g) from inlet gas stream.
In the process, only physical absorption will occur. The solute used is hydrogen chloride
gas, HCl(g) while the chemical substance used to absorb HCl(g) is hydrochloric acid,
HCl(l) which is also known as the solvent in the process. The main objective of the
absorption is absorb the hydrogen chloride gas from the gas inlet stream in order to
recover the hydrogen chloride gas to be as the raw product of the process of HCl(l)
again. This is an economic step to save cost by not wasting the outlet stream that can be
recycled again as our raw product
Upon the physical absorption of HCl(g) by HCl(l) which is an exothermic process, the
temperature of both the outlet stream rises and is calculated to be 53.5 0C by the
calculation in energy balance. The outlet gas stream then flows to the dryer in order to
further process the stream in order to get 17.61kmol/hr of pure chlorine gas which is
our desired product. Meanwhile, the outlet liquid stream will enter a splitter which will
subdivide the stream into two. One of the divided stream will be purged out as the
product while the other large portion of the liquid stream will be recycled back to the
expeller as the inlet feed again.

The steps in designing a packed column are:

a) Choose suitable choice and type of packing
b) Determine the column height required for the specified separation
2 Methods:

Method 1:

Z = HETP*Number of equivalent plates

Method 2:

Z = HOG * NOG

c) Determine the column diameter to handle liquid and vapor flow rates.

6.4.1 Choice of packing

Packed column is chosen for the HCl absorber rather than plate column due to the
following reasons:

Packed columns are suitable for high liquid flow rate.

Liquid hold-up is low for packed column to handle corrosive HCl solution
The pressure drop per equilibrium stage (HETP) can be lower for packing than
plates.

6.4.2 Type of packing

The principal requirements of a packing should consider the following criteria:

Promote uniform liquid distribution on the packing surface.

Have an open structure which provides low resistance to gas flow
Promote uniform vapor gas flow across the column cross-section
Provide a large surface area for mass transfer to occur between the gas and
liquid

6.4.3 Selection of Type and Sizes of Packing

In the selection of the type and sizes of the packed column HCl absorber, a few
conditions are needed to be achieved. Basically, we need to increase the overall
performance of the packed column absorber. All the same, the designing cost and
operating cost of the packed column absorber also have to be brought into
considerations. Hence, the objectives functions of designing the packed column HCl
absorber are:

(i) Maximizing the overall performances of the column

(ii) Minimizing the total cost
Other than these two aspects, we also have to consider the safety issues of the design. It
is essential to ensure that there is a low inventory of the toxic and flammable liquids in
the packed column. Besides, it is necessary to ensure that the design is environmental
friendly and will not cause any pollution to the environment.

2 General Type of Packings

1. Random Packing
It is a type of packing materials that have many shapes such as rings, saddles and
proprietary shapes. They are dumped into the packed column absorber and
being arranged randomly. For random packing, a high liquid load is suitable to be
used. Other than that, a vacuum operation is needed.
.
So in the design of packed column HCl absorber, random packing is chosen over
structured packing. It is due to the fact that random packing is more economical
compared to structured packing. Likewise, it is preferable to use the random
packing since there is no significant pressure drop in the packed column HCl
absorber.
There are several types of geometry and structure of random packing. After
selecting the structure of the random packing, we have to choose the material of
the packing such as plastics, ceramics or etc. There are generally five common
types of structure in the random packing.
a)
b)
c)
d)
e)

Raschig rings
Cascade rings
Berl saddle
Pall rings
Intalox Saddle

Intalox Saddle

Figure: Ceramics Intalox Saddle

Sources: Intalox Saddle Ring, Retrieved on 1/6/2015 from http://www.ceramichoneycombs.com/tower_packing/Intalox_Saddle_Ring_Tower_Random_Column_
Packing.htm

Hence, in the design of a packed column HCl absorber, ceramic Intalox Saddle is chosen.
The reason of choosing the ceramic Intalox Saddle:
The advantages of using Ceramics Intalox Saddle:

Ceramic will not cause any significant pollution (best choice to handle
corrosive liquid. In this case is hydrochloric acid used as the solvent
which is a corrosive liquid.
Intalox saddle increase the free and improves the liquid distribution
characteristics.
High level of stability
Relatively low cost
Smooth surface impact with high chemical resistance

Figure: Design data from various packing

Source: Pg 591, Coulson & Richardson Chemical Engineering_Volume 6

The specification of Intalox Saddles(Ceramics) chosen

Design Data

Value

Size
Bulk Density
Surface Area
Packing factor, Fp

38mm
625 kg/m3
194m2/m3
170m-1

Lin = 217.63 kmol/h

Gout = 217.63 kmol/h

Xin = 0.1221

yout = ?

HCl Absorber

Lout = 187.65 kmol/h

Gin = 87.28 kmol/h

Xout = 0.2179

yin = 0.4

By component balance
Gin yin + Lin xin = Gout yout + Lout xout
87.28kmol/h (0.4) + 217.63kmol/h (0.1221) = 217.63kmol/h (yout ) + 187.65 kmol/h
(0.2179)

yout = 0.23
Plotting equilibrium
y= Kx
where

Hence

K=

Apply Antoine Equation to obtain value of saturated pressure at T = 53.5C or

326.5K

()

At 326.5 K
Antoine's Constant are as follows:
Antoines Constant

Value

3.4531

1068.4

1.754

()

Psat = 1.5791 bar

Psat = 1.6 atm
NOMENCLATURE:
x = solute concentration in the liquid
y = solute concentration in the gas

1 6
1

1.6* x

Equilibrium line
x
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1

y
0.16
0.32
0.48
0.64
0.8
0.96
1.12
1.28
1.44
1.6

Operating line
For x
xin
xout

x
0.1221
0.2179

xin
xout

y
0.21
0.4

For y

y VS x for operating line and equilirbium line for HCl

Absorption
0.6

Equilibrium data
Operating line

0.5
y = 1.6x
y = 1.8989x - 0.0102

0.4

0.3

0.2

0.1

0
0

0.05

0.1

0.15

0.2

0.25

0.3

0.35

Figure 1: y vs x for Operating line and Equilibrium line for HCl Absorption

Number of transfer unit (NTU) = 4 theoretical plates

There are two methods of calculating the height of the packings:

1. Z = HETP (Height of Equivalent Theoretical Plates) x NTU (Number of Transfer
Units)
2. Z = HOG * NOG

6.4.4 Method 1: HTU/HETP * NTU

Step 1 : Selecting a type and size of packing
Ceramic Intalox Saddle ring is selected with packing factor of 170 m^-1 with improved
liquid distribution characteristics.

Step 2 : Determine the column diameter

In a packed column HCl absorber, there will be pressure drop. Basically, a packed
column absorber is designed to achieve the best absorption for hydrochloric acid to
absorb hydrogen chloride gas. Based on the research, the optimum pressure drop for
the design parameter is in the range of 40mm of water/meter of packed height until
80mm of water/meter of packed height. Thus, in the design of HCl absorber, we choose
a pressure drop of 42mm of water/meter of packed height which is in the range of 40 to
80 mm of water/meter of packed height.
On the other hand, for the flooding percentage, the satisfactory result is in the range of
60% to 80% of flooding.

Figure: Generalized pressure drop correlation

Calculating the parameters required to calculate column diameter

a) Gas Flow Rate of HCl (g) , Vw

87 28

1
3600

36 5
1

= 0.8849 kg/s

Liquid Flow Rate of HCl (l), Lw

217 63

1
3600

= 2.2065 kg/s

b) Specifications of parameters:

36 5
1

Parameter

Value

;1

Density of Hydrogen Chloride gas,

1.49

Density of Hydrochloric acid,

1.017

c) From Sherwood Correlation and by referring to the Figure: Generalized Pressure

Drop
Correlation
Chart

FLV =

x-axis :

( ) =

) = 3.01816

From Generalized Pressure Drop Correlation, when the value of x-axis (FLV ) =
3.01816, the value of correlated value of K4 is equal approximately 0.115
)

13 1(

y-axis:

To calculate mass flux rate of hydrogen chloride gas (

(

13 1

=(

0 115 1 49 ( 1 49;1 017)

0.608 kg/m^2*s

13 1 170

0 8849

Column Area required = 0 608

d) Calculating the minimum diameter of the Column

Column Area =

^2
4

Diameter =

For safety purpose, diameter is rounded off to 1.50m

= 1.36m

e) Recalculating the column area with diameter, D = 1.50m

Column area =

15
4

= 1.7671m

f) Packing size to column diameter ratio

1 7671

Packing size to column diameter ratio = 38

= 46.5

10

Flooding Velocity

a) Design for a pressure drop of 42 mm H2O / m packing

By refering to Figure 11.44: Generalized Pressure Drop Correlation
K4 at 42 mm H2O / m packing
K4 at flooding

b) Percentage flooding =

0.115
0.185

77.8%

satisfactory ( Between 60%

to 80%)

c) A larger packing size could be considered

% flooding at selected diameter = 77.8 * 1.4545/1.7671 = 64.04%

(satisfactory- Between 60 to 80%)

d) Calculation of Pressure drop

Kister and Gill Equation: (From McCabe & smith 5th edition)

07
07

= 4.188inch H2O/ ft
= 106.38mm H2O/m packing
Could consider reducing column diameter

Step 3 : Determine the column height

For absorption of all packing size, HETP is expresses as 1.83m by each theoretical plate

Z = HTU x NTU
= 1.83m/theoretical plates * 4 theoretical plates
Z = 7.32m

6.4.5 Method 2: Z= HOG * NOG

HOG in HCl Absorber
Prediction of height of transfer units by Ondas Methods
It is an useful correlation for the film mass-transfer coefficients
and
and the
effective wetted area of the packings, , which can be used to calculate
and .
The equation for the effective area is:
1. Calculating the effective area,
0 75

* (

)0 1 * (

65 95

(1 017

0 0059
1 87

);0 05 * (

0 75

61
194

01

10

194

0 05589
1 017

) 02]

194 ;0 05
9 81

) 02]

By solving the equation,

Effective area,

2. Calculating HOG
2.1 For the liquid phase mass-transfer coefficient:
(

(1 87

1 017

)
9 81

10
;3 0 4

) =0.0051* (

=0.0051*

( 193 32

0 05589
1 87

10

(a

)0 4

1 87

10

1 017 0 2272

Liquid phase mass-transfer coefficient,

;6

kmol/sm^2 bar

* (

2.2 For the gas-phase mass-transfer coefficient

=

0 08314 326 5
194 2 272

10

07

0 8045

0 05589

07

194 0 05589

);2 0

(a

1 49 0 2272

;3 ;2 0

;5

Gas phase mass-transfer coefficient,

2.3 Calculate mass flux rate of the gas vapor,

0 8849
11

= 0.8045

0 8045
36 5

0 05589
36 5

= 0.02204

= 1.392 x 1

;3

2.4 Film transfer unit heights in gas phase,

= 2 95

0 02204
10

193 92 1 013

= 3.7974m

2.5 Film transfer unit heights in liquid phase,

=

1 392
1

10

10

193 92

= 4.58m

2.6 Overall height of a transfer unit ,

= 3.7974 + 3.038 ( 0.2576)

= 4.58 m

3. Calculating NOG
Number of overall gas-phase transfer units,
Where

is the log mean driving force, given by

( 1)
2

= 0.4 0.19
= 0.21

= 0.23 0.19
= 0.04

0 21; 0 04

= 0.1024

Number of overall gas-phase transfer units,

0 4 0 23

0 1024

= 1.6582

4. Calculate the height of packing column, Z

Z=

= 4.58 * 1.6582

= 7.59 m

Compare the value with the value of packing of column height found from
Method 1 and Method 2

Z= Number of theoretical plates * Height of equivalent theoretical plates

= 4 * 1.83m
= 7.32 m

The percentage error of Z from two formula

% error =

7 59 7 32
7 59

= 3.56 %

The toleration set is to be within 5% error. The small percentage error of 3.56%
which is lower than tolerance value of 5% shows that the height of packed
column is roughly about 7.5 m which proves the value accurate and trustable.
6.4.6 Packing support
The function of the packing support plate is to carry the weight of the wet packing,
while at the same time allowing free passage of the gas and liquid.
A small diameter simple grid & perforated support is chosen. There are two packing
supports in the packed column HCl absorber. One packing support is needed to carry
the weight of wet packing at the top while the other one is required at the bottom. The
height of one support are designed to be 0.5m each. Hence, two packing supports
contributed to 1.0m to the total height of the unit operation.

6.4.7 Liquid Distributor

The good and satisfactory type of packed column is dependent on maintaining a

uniform flow of liquid throughout the column without creating significant pressure
drop. In this case, a good initial liquid distribution is very important. Since the column
diameter of the packed column HCl absorber is 1.50m which is considered quite large, a
trough-type distributor is used to give good liquid distribution with a large free area for
gas flow.
There is only one liquid distributor required to distribute evenly for the inlet liquid. The
liquid distributor is designed to be 0.8m.

6.4.8 Wetting Rate

The packing wetting rate is checked for the packed column HCl absorber to ensure that
it is above the minimum recommended by the packing manufacturer.

Since wetting rate of 0.00213 3 2

is higher than the recommendation of Kister
3
2
(1992) that is 0.0014
, the column diameter of 1.50m is logic.
Total height of the Unit Operation
The total height of the unit operation = height of packings + height of liquid distributor +
height
of packing supports + Spacing between each part
The spacing between each part is designed to be 1.95m for the top and 1.95m for the
bottom.
Respective part of HCl Absorber

Height(m)

Packings

7.50

Liquid Distributor

0.8

Packing supports

1.0

Spacing between each part

3.9

Total

13.2

Hence, the total height of the HCl absorber is 13.2m.

6.4.9 Mechanical Design

External Diameter
The wall thickness is designed to be 0.2m to allow for heat transfer to occur
effectively.
Hence, the outer diameter of the HCl absorber is
Outer diameter = 1.5m + 2(0.2m) = 1.9m

6.4.10 Design of two P&ID controller to control the process

Since the solvent used to absorb hydrogen chloride is hydrochloric acid which is
a corrosive that might corrodes the inner surface of the absorber in a long terms,
we have to control and maintain properly the flow rate of the hydrochloric acid
flowing into the absorber column. Hence, a flow controller or a level instrument
is inserted beside the inlet outlet circulated at the bottom of the absorber
column.
Besides, the outlet temperature of the gas to the dryer also have to be maintained
at a temperature so that it is 53.5C which is suitable for the process for
subsequent drying. Hence, a temperature controller is inserted to maintain the
outlet temperature by controlling the flow rate of inlet liquid stream. Once the
outlet temperature of the gas stream falls outside the desired value, the response
will be received by temperature sensor and signal will be sent to the inlet liquid
to control/maintain the temperature by manipulating the flow rate of the inlet
stream.

Vapor outlet

Liquid inlet

LT

LC

Absorption
Column

Vapor inlet

Liquid outlet
TC

TT

Symbol for Nomenclature

1.
2.
3.
4.
5.
6.

LTTTLCTC-

Normal flow line

Flow line controlled by the controller
Level detector
Temperature sensor
Level Controller
Temperature Controller

6.4.11 Design Summary

Chemical Engineering Design Parameter
Specifications
Column Height

7.50m

Height of absorber unit operation

13.2 m

Column Diameter

1.50m

Type of packings used

Intalox Saddle-Ceramics

Packing support

Simple grid & perforated support

Liquid Distributor

Trough-type liquid distributor

Level Controller

Flow controller/ Level Instrument

Mechanical Engineering Design

Column Outer Diameter

1.9m

6.5

Dryer

6.5.1 Introduction

Drying Process of Chlorine

The purpose of drying is to absorb the water vapour content of the chlorine gas
coming from the chlorine cooling in order to prevent corrosion, formation of chlorine
hydrate and hydrous iron chloride. Wet Chlorine gas can be hazardous and highly
reactive. The mechanism of the drying process is based on the adsorption of the
residual water vapour using concentrated sulfuric acid with a min. concentration of
98% H2SO4. Through the adsorption of the water vapour, the acid is diluted to about
70 % H2SO4 and the moisture content in the wet chlorine gas is reduced. The second
dryer will further diluted the acid to 30% H2SO4.The drying system is improved by the
using two columns connected in series. This is due to the heat of dilution produced in
the column and caused the temperature of acid increases. The absorbing efficiency
decreases with temperature.
An intercooler is placed between the columns to cool down the acids before going
through the second adsorbing process. The chlorine gas leaving the packed column is
finally dried in the tray column. The high adsorption efficiency results from the size,
shape and numbers of the impingement trays. The sulphuric acid is maintained in 20
0C for optimum absorbing performance.
Random Packed Column
The column is filled with random dumped packing to create a random packed column
or with structured packing sections. Inside the column, the liquids tend to wet the
surface of the packing and when the vapours pass across this wetted surface, mass
transfer of certain particles can be take place. In this case, the liquids are referring to
the sulphuric acid while the vapours are the water content in the wet chlorine gas.
Packing material can be used instead of trays to improve separation performance in
absorbing columns. Packing offers the advantage of a lower pressure drop across the
column when compare to tray column, which is an advantage for process operated
under vacuum. Differently shaped packing materials have different surface factors and
void space between the packing. Both of these factors affect packing performance as
well as the overall process efficiency.

Calculating the stream properties (Preliminary Calculation)

Stream 30

Overall mass balance

Gas vapour out (Top Product)

Selection of the type and the size of column packing materials
:

The packing material are

Vapour stream (Between

Columns) V1

2

2
2
2

2

2
2
2

=0.2623454
=2.529x10-5
=3.35x10-5
=0.0374804
=0.7001153

Stream 28
Liquid Feed (98% Sulfuric
Acid)
:

=0.232094
=2.237x10-5
=0.1153412
=0.0331585
=0.6193839

2 SO4 =0.8993
2 =0.1007

Intercooler Heat Duty:

67759.86 kJ/hr
Liquid stream (Between Columns)
L1

From stream 27

Gas vapour feed

2

2
2
2

Stream 29

2 SO4 =0.29983
2 =0.70017

Liquid Product (Bottom Product)

=0.1513
=1.5x10-5 :
=0.42599
=0.01891

=0.40378
2 SO4 =0.0729178
2 =0.9270822

Overall Mass Balance(Appendix)

For the First Dryer
H2O Component mass balance

For the Second Dryer

H2O Component mass balance

Stream Properties Table

Stream
Total Mass(kg/hr)
Total
Mole(kmol/hr)

27
3558.97

30
2659.01

V1
2817.82

117.69

67.69

76.52

Mass Of Water
Mole
Mole Fraction

900.00
50.00
0.42

0.04
2.27E-03
3.35E-05

158.86
8.83
0.12

Mass Of Cl2
Mole
Mole Fraction

1260.87
17.76
0.15

1260.87
17.76
0.26

1260.87
17.76
0.23

Mass Of HCl
Mole
Mole Fraction

0.06
1.71E-03
1.45E-05

0.06
1.71E-03
2.53E-05

0.06
1.71E-03
2.24E-05

Mass Of O2
Mole
Mole Fraction

71.04
2.54
0.02

71.04
2.54
0.04

71.04
2.54
0.03

Mass Of N2
Mole
Mole Fraction

1326.99
47.39
0.40

1326.99
47.39
0.70

1326.99
47.39
0.62

Stream
Total Mass(kg/hr)
Total Mole(kmol/hr)

28
397.04
4.41

29
1297.00
54.41

L1
555.86
13.23

Mass Of Water
Mole
Mole Fraction

389.10
3.97
0.90

907.90
50.44
0.93

166.76
9.26
0.70

Mass Of Sulfuric Acid

Mole
Mole Fraction

7.94
0.44
0.10

389.10
3.97
0.07

389.10
3.97
0.30

Overall Energy Balance(Appendix)

Table of thermodynamics properties of streams
Stream
27
30
V1
28
29
L1

Temperature(0C)
28.00
28.00
28.00
20.00
94.73
96.99

Calculation of internal Cooler heat duty

Pressure(bar)
1
1
1
1
1
1

6.5.2 Selection of a type and size of column packing materials

In the case, random packing materials are used such as such as rings, saddles and
proprietary shapes, which are dumped into the column and taking up a random
arrangement.
The packing material is selected based on the requirement for the process in order to
provide a large surface area (To ensure high interfacial area between the gas and liquid)
and promote uniform vapour gas flow across the column cross-section.

Table 6.5.2: The design data for various random packing

In this dryer column, Raschig rings is chosen, this is because:
a) Raschig rings has Small pressure drop
b) Raschig rings promote wetting and it is cheap
c) Ceramic packing is the first choice for corrosive liquids especially sulfuric acid

Type of packing
size(mm)
packing factor, Fv
a(m2/m3)

Raschig rings
51
210
95

6.5.4 Determine the column Diameter

Using Generalised pressure drop correlation in Richardson and Coulson chart, the

Blue line-First
Column
Brown lineSecond
Column

diameter of the column can be determined.

For First dryer column
Viscosity of liquid, L 10.5mPa.s
Density of liquid, L 1610.5 kg/m3
Density of gas, v

30.696 kg/m3

From the chart, K4 = 1.3

)
01
2

)(

)(

)
01

For second dryer column

Viscosity of liquid, L 26.7mPa.s
Density of liquid, L 1840kg/m3
Density of gas, v

37.410 kg/m3

From the chart, K4 = 0.9

)
01
2

)(

)(
(

)
01

6.5.5 Determine the column height

Peters (2002) suggests that this same enrichment of the vapor will occur in a certain
height of packing, which is termed the height equivalent of a theoretical plate (HETP). In
practice, the HETP concept is used to convert empirically the number of theoretical
stages to packing height.

Table of HETP for Distillation Design by Henry Kister (McGraw-Hill, ISBN 0-07-034909-6)

For first column dryer

For second column dryer

6.5.6 Mechanical design for Two Step Packed column Dryer

Design Pressure, PD
A vessel must be able to withstand the maximum pressure to which it is subjected
during the operation. A safety factor of 5 to 10% above the normal working pressure is
recommended to avoid spurious operation and explosion during minor process upsets.
(

Design Temperature, TD
As mentioned before, the maximum design temperature must be including a 10% safety
factor to cover uncertainties in temperature prediction due to the external factor such
as surrounding temperature influences.

Material of Construction
Selection of a suitable material is important as we need to consider the corrosive
properties of the stream as well as the sustainability and the compatibility of the
material with the process environment. The austenitic stainless steel 304 is chosen
since it is most common material used as the construction material.
Welded Joint Factor, J
The strength of a welded joint is relative to the type of joint and the quality of the
welding. Welded joint factor is taken as 1.0 which implies that the joint is equally as
strong as the virgin packing and plates.
Corrosion Allowance
The corrosion allowance is defined as the additional thickness of metal added to allow
for material lost by corrosion and erosion, rusting or scaling. The allowance is
determined based on the experience or from the literature review from the previous
hand on operation. For stainless steel, severe corrosion is not expected but certain
tolerance is needed to be consider as the operation involved sulphuric acid which is
highly corrosive, the corrosion allowance of 2.0 mm is used.

Total column height

The total column height is included the height of the packing material, top section
column head and bottom section column head.

Design Stress, FD
Design stress are calculated to ensure that the material could be expected to withstand
maximum stress without failure under standard test conditions. The design stress factor
of 1.5 is chosen for austenitic stainless steel. Thus, the design stress at in this column is
2.115 N/mm2.

Cylindrical Column Shell Thickness

Cylindrical Column shell thickness required be thicker than theoretical estimation in
order to resist internal pressure can be determined from the following equation:

First Column

(
( ) (

Second Column

) (
)

(
( ) (

) (
)

6.5.7 Design summary

Gas feed flow rate(kmol/hr)

Gas product flow
rate(kmol/hr)
Liquid feed flow
rate(kmol/hr)
Liquid Product flow
rate(kmol/hr)
Packed column height(m)
Total Column Height(m)
Packed column Diameter(m)
Packed column area(m2)
Stream Pressure(bar)
Design Pressure(kPa)
Design Temparatureliquid(0C)
Design Temparaturegas(0C)
Design Stess(N/mm2)
Packing Material
Column Material
Welded Joint Factor
Corrosion Allowance(mm)
Inner Column Diameter(m)
Minimum Column Thickness
(mm)
Outer Column Diameter(m)

First column
117.69
76.52

Second column
76.52
67.69

4.41

13.23

13.23

54.41

1.83
3.03
0.37
0.11
1
111.46
106.689
30.8
2.115
Raschigs Ring
austenitic stainless steel
304
1
2
0.37
10.013

1.83
3.03
0.34
0.09
1
111.46
106.689
30.8
2.115
Raschigs Ring
austenitic stainless
steel 304
1
2
0.34
9.2014

0.38

0.35

Appendix
Equlibrium data of the water-sulfuric acid binary system
x
0.62
0.64
0.66
0.68
0.70
0.72
0.74
0.76
0.78
0.80

y
0.269
0.354
0.450
0.550
0.646
0.731
0.802
0.858
0.900
0.931

x
0.82
0.84
0.86
0.88
0.90
0.92
0.94
0.96
0.98
1.00

y
0.953
0.968
0.978
0.985
0.990
0.993
0.996
0.997
0.998
0.999

1.400

1.200

y = 1.7693x - 0.6157

1.000

0.800

0.600

0.400

0.200

0.000
0.60

0.65

0.70

0.75

0.80

0.85

0.90

0.95

1.00

1.05

Calculation for the McCabe-Thiele analysis of FIRST absorbing column

Average Molar Mass of gas=
Inlet Feed Temperature=
Operating Pressure=
Density of Gas--PMr/RT=
Mole of water in exiting gas
stream=
water to be absorbed=
Equation of equilibrium line

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

30.326 kg/kmol
28 oC
25 atm
30.696 kg/m3
8.825 kmol/hr
41.175 kmol/hr

Operating line
x

y
0.927
0.700

0.425
0.120

y
0.000
0.177
0.354
0.531
0.708
0.885
1.062
1.239
1.415
1.592
1.769

1.200
y = 0.5617x + 0.6328

1.000
0.800
0.600
0.400
0.200
0.000
0

0.1

0.2

0.3

0.4

-0.200

Number of theoretical step= 1

Slope/Gradient= 0.562
New Gradient= 0.843
Amount of Liquid flow rate = 106.917 kmol/hr
Recheck for G(vapour flow rate):
Gout= liquid flow rate / new gradient = 126.897 kmol/hr
Goriginal= 117.690kmol/hr
Kister and Gill equation

0.5

0.6

0.7

07

Calculation for the McCabe-Thiele analysis of SECOND absorbing column

Average Molar Mass of gas=
Inlet Feed Temperature=
Operating Pressure=
Density of Gas--PMr/RT=
Mole of water in exiting gas
stream=
water to be absorbed=
Equation of equilibrium line

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

36.959 kg/kmol
28 oC
25 atm
37.410 kg/m3
0.002 kmol/hr
8.823 kmol/hr

Operating line
x

y
0.700
0.100

0.120
0.000

y
0.000
0.177
0.354
0.531
0.708
0.885
1.062
1.239
1.415
1.592
1.769

1.200
y = 0.5617x + 0.6328

1.000
0.800
0.600
0.400
0.200
0.000
0

0.1

0.2

0.3

0.4

-0.200

Number of theoretical step= 1

Slope/Gradient= 1.517
New Gradient= 2.275
Amount of Liquid flow rate = 116.883 kmol/hr
Recheck for G(vapour flow rate):
Gout= liquid flow rate / new gradient = 51.376 kmol/hr
Goriginal= 76.516kmol/hr

0.5

0.6

0.7

Kister and Gill equation

07

Overall Energy balance calculation for Two Steps Packed Column Dryer
Appendix G: Heat Capacity Equation
= a + b(T) + c(T)^2 +d(T)^3

dT

Component

HCl

0.02913

-1.341E-06

9.715E-09

-4.335E-12

Cl2

0.0336

0.00001367

-1.607E-08

6.473E-12

H2O(g)

0.03346

0.00000688

7.604E-09

-3.593E-12

N2

0.029

2.199E-06

5.723E-09

-2.871E-12

O2

0.0291

0.00001158

-6.076E-09

1.311E-12

H2O(l)

0.0754

Calculation of specific enthalpy at different temperature

, ( )

Temp Ref(Deg C)=

0.00

Specific enthalpy, H (kJ/kmol)

T(Deg C)

HCl

Cl2

H2O

N2

O2

H2O(l)

58.00

1689.50

1949.20

1940.88

1682.06

1688.14

4373.20

53.50

1558.42

1797.97

1790.29

1551.56

1557.16

4033.90

29.00

844.75

974.60

970.44

841.03

844.07

2186.60

28.00

815.62

940.99

936.98

812.03

814.96

2111.20

16.00

466.07

537.71

535.42

464.02

465.69

1206.40

10.00

291.29

336.07

334.63

290.01

291.06

754.00

-20.00

-582.59

-672.14

-669.27

-580.02

-582.12

-1508.00

Temperature of aqueous sulfuric acid

Temp Ref=
0.00 Deg C
enter=
20.00 Deg C
exit=
96.99 Deg C
Specific heat capacity of aqueous sulfuric acid
wt%
specific heat capacity
Sulfuric acid(aq),T :
cal/g.K
kJ/kg.K
kJ/kmol.K
5 to 300 K
98.00
0.33
1.37
0.01
70.00
0.47
1.98
0.02
40.00
0.68
2.84
0.03
30.00
0.77
3.23
0.03
15.00
0.88
3.67
0.04
Specific heat capacity of water in 98% sulfuric acid outlet (kJ/kmol)
1508.00 kJ/kmol
Specific heat capacity of water in 30% sulfuric acid outlet (kJ/kmol)
7313.30 kJ/kmol
Heat of Dilution due to Sulfuric acid(98% to 70%)
-65.00 Btu/lb
-151.19 kJ/kg
Energy Balance in 2nd Dryer
Inlet
Outlet
Sulfuric acid 98% , 20 Deg C
Sulfuric acid 70%
total mass=
397.04 kg/hr
total mass=
555.86 kg/hr
total mole=
4.41 kmol/hr
total mole=
13.23 kmol/hr
Mass
Mass
H2SO4=
389.10 kg/hr
H2SO4=
389.10 kg/hr
Mole=
3.97 kmol/hr
Mole=
3.97 kmol/hr
Mole
Mole
fraction=
0.90
fraction=
0.30
Mass H20=
7.94 kg/hr
Mass H20=
166.76 kg/hr
Mole=
0.44 kmol/hr
Mole=
9.26 kmol/hr
Mole
Mole
fraction=
0.10
fraction=
0.70
Total
Total
Enthalpy=
666.37 kJ/hr
Enthalpy=
8933.43 kJ/hr
stream, 28 Deg C
stream,28 Deg C
total mass=
2817.82 kg/hr
total mass=
2659.01 kg/hr
total mole=
76.52 kmol/hr
total mole=
67.69 kmol/hr
mass of
mass of
water=
158.86 kg/hr
water=
0.04 kg/hr
Mole=
8.83 kmol/hr
Mole=
0.00 kmol/hr
Mole
Mole
fraction=
0.12
fraction=
0.00
mass of Cl2=
1260.87 kg/hr
mass of Cl2=
1260.87 kg/hr
Mole=
17.76 kmol/hr
Mole=
17.76 kmol/hr
Mole
0.23
Mole
0.26

fraction=
mass of HCl=
Mole=
Mole
fraction=
mass of O2=
Mole=
Mole
fraction=
mass of N2=
Mole=
Mole
fraction=
Enthalpy=
Total
Enthalpy=

fraction=
0.06 kg/hr
mass of HCl=
0.00 kmol/hr
Mole=
Mole
0.00
fraction=
71.04 kg/hr
mass of O2=
2.54 kmol/hr
Mole=
Mole
0.03
fraction=
1326.99 kg/hr
mass of N2=
47.39 kmol/hr
Mole=
Mole
0.62
fraction=
65533.32 kJ/hr
Enthalpy=
Total
66199.69 kJ/hr
Enthalpy=
Change of
Enthalpy=
0.00 kJ/hr
Intercooler Heat duty:
67759.86 kJ/hr

Temperature of aqueous sulfuric acid

enter=
20.00 Deg C
exit=
94.73 Deg C
Specific heat capacity of aqueous sulfuric acid
wt%

Temp Ref=

0.06 kg/hr
0.00 kmol/hr
0.00
71.04 kg/hr
2.54 kmol/hr
0.04
1326.99 kg/hr
47.39 kmol/hr
0.70
57266.25 kJ/hr
66199.69 kJ/hr

0.00 Deg C

Boiling point of
H2SO4
287 deg F

specific heat capacity

cal/g.K
kJ/kg.K
kJ/kmol.K
98.00
0.33
1.37
0.01
70.00
0.47
1.98
0.02
40.00
0.68
2.84
0.03
30.00
0.77
3.23
0.03
15.00
0.88
3.67
0.04
Specific heat capacity of water in 98% sulfuric acid outlet (kJ/kmol)
1508.00 kJ/kmol
Specific heat capacity of water in 30% sulfuric acid outlet (kJ/kmol)
7142.41 kJ/kmol
Heat of Dilution due to Sulfuric acid(70% to 30%)
-340.00 Btu/lb
-790.84 kJ/kg
Energy Balance in First Dryer
Inlet
Outlet
Sulfuric acid 70% , 20 Deg C
Sulfuric acid 30%
total mass=
555.86 kg/hr
total mass=
1297.00 kg/hr
total mole=
13.23 kmol/hr
total mole=
54.41 kmol/hr
Mass
389.10 kg/hr
Mass
389.10 kg/hr

H2SO4=
Mole=
Mole
fraction=
Mass H20=
Mole=
Mole
fraction=
Total
Enthalpy=

3.97 kmol/hr
0.30
166.76 kg/hr
9.26 kmol/hr
0.70

H2SO4=
Mole=
3.97
Mole
fraction=
0.07
Mass H20=
907.90
Mole=
50.44
Mole
fraction=
0.93
Total
Enthalpy=
52551.78
stream,28 Deg C
total mass=
2817.82
total mole=
76.52
mass of
water=
158.86
Mole=
8.83
Mole
fraction=
0.12
mass of Cl2=
1260.87
Mole=
17.76
Mole
fraction=
0.23
mass of HCl=
0.06
Mole=
0.00
Mole
fraction=
0.00
mass of O2=
71.04
Mole=
2.54
Mole
fraction=
0.03
mass of N2=
1326.99
Mole=
47.39
Mole
fraction=
0.62
Enthalpy=
65533.32
Total
Enthalpy=
118085.10

13972.15 kJ/hr
stream, 28 Deg C
total mass=
3558.97 kg/hr
total mole=
117.69 kmol/hr
mass of
water=
900.00 kg/hr
Mole=
50.00 kmol/hr
Mole
fraction=
0.42
mass of Cl2=
1260.87 kg/hr
Mole=
17.76 kmol/hr
Mole
fraction=
0.15
mass of HCl=
0.06 kg/hr
Mole=
0.00 kmol/hr
Mole
fraction=
0.00
mass of O2=
71.04 kg/hr
Mole=
2.54 kmol/hr
Mole
fraction=
0.02
mass of N2=
1326.99 kg/hr
Mole=
47.39 kmol/hr
Mole
fraction=
0.40
Enthalpy=
104112.95 kJ/hr
Total
Enthalpy=
118085.10 kJ/hr
Change of
Enthalpy=
0.00 kJ/hr
Intercooler Heat duty:
360265.01 kJ/hr

kmol/hr

kg/hr
kmol/hr

kJ/hr
kg/hr
kmol/hr
kg/hr
kmol/hr

kg/hr
kmol/hr

kg/hr
kmol/hr

kg/hr
kmol/hr

kg/hr
kmol/hr

kJ/hr
kJ/hr

Overall Mass balance calculation for Two Steps Packed Column Dryer
1st Dryer Column
in(cooler)
total mass= 3558.97
total mole= 117.69
mass of water= 900.00
Mole=
50.00
Mole fraction=
0.42

kg/hr
kmol/hr
kg/hr
kmol/hr

mass of Cl2= 1260.87 kg/hr

Mole=
17.76 kmol/hr
Mole fraction=
0.15
mass of HCl=
0.06 kg/hr
1.71EMole=
03 kmol/hr
1.45EMole fraction=
05
mass of O2=
71.04 kg/hr
Mole=
2.54 kmol/hr
Mole fraction=
0.02
mass of N2= 1326.99 kg/hr
Mole=
47.39 kmol/hr
Mole fraction=
0.40

out(sulfuric acid)
total mass= 1297.00
total mole=
54.41
mass of water= 907.90
Mole=
50.44
Mole fraction=
0.93
mass of sulfuric
acid= 389.10
Mole=
3.97
Mole fraction=
0.07

Between the Dryer Columns

out(sulfuric acid + water)
out(Cl2)
70% H2SO4
total mass= 555.86 kg/hr
total mass= 2817.82
total mole=
13.23 kmol/hr
total mole=
76.52
mass of water= 166.76 kg/hr
mass of water= 158.86
Mole=
9.26 kmol/hr
Mole=
8.83
Mole fraction=
0.70
Mole fraction=
0.12
mass of sulfuric
acid= 389.10 kg/hr
mass of Cl2= 1260.87
Mole=
3.97 kmol/hr
Mole=
17.76
Mole fraction=
0.30
Mole fraction=
0.23
mass of HCl=
0.06
1.71EMole=
03
2.24EMole fraction=
05
mass of O2=
71.04
Mole=
2.54
Mole fraction=
0.03
mass of N2= 1326.99
Mole=
47.39
Mole fraction=
0.62

kg/hr
kmol/hr
kg/hr
kmol/hr

kg/hr
kmol/hr

kg/hr
kmol/hr
kg/hr
kmol/hr

kg/hr
kmol/hr
kg/hr
kmol/hr

kg/hr
kmol/hr
kg/hr
kmol/hr

2nd Dryer Column

out(sulfuric acid + water)
out(Cl2)
98 % H2SO4
total mass= 397.04 kg/hr
total mass= 2659.01
total mole=
4.41 kmol/hr
total mole=
67.69
mass of sulfuric
acid= 389.10 kg/hr
mass of water=
0.04
2.27EMole=
3.97 kmol/hr
Mole=
03
3.35EMole fraction=
0.90
Mole fraction=
05
mass of water=
7.94 kg/hr
mass of Cl2= 1260.87
Mole=
0.44 kmol/hr
Mole=
17.76
Mole fraction=
0.10
Mole fraction=
0.26
mass of HCl=
0.06
1.71EMole=
03
2.53EMole fraction=
05
mass of O2=
71.04
Mole=
2.54
Mole fraction=
0.04
mass of N2= 1326.99
Mole=
47.39
Mole fraction=
0.70

kg/hr
kmol/hr
kg/hr
kmol/hr

kg/hr
kmol/hr
kg/hr
kmol/hr

kg/hr
kmol/hr
kg/hr
kmol/hr

6.6
6.6.1

Heat Exchanger
Calculation of Area

As we have calculated the mass flowrate and other required parameters from the mass
balance and also the energy balance.
COOLING WATER

T outlet(C)
T inlet(C)

COMPONENTS

20
13

T (C)inlet
T (C)outlet

Mass fraction
Cp(kJ/kmol C)
Density(kg/m^3)
Viscosity(Ns/m^2)
Thermal Conductivity
(W/m.K)
Mass flowrate(kg/h)

Mass flowrate(kg/h)
Cp(kJ/kmol C)
Density(kg/m^3)
Viscosity(Ns/m^2)
Thermal Conductivity
(W/m.K)

3558.9676
4.187000
1000.0000
0.001000
0.580000

53.5
28

H20
0.252882323
4.183000
1000.000000
0.001187

Cl2
0.354281
0.034286
2.994000
0.000015

HCl
0.000018
0.029085
1.528000
0.000018

O2
0.019961
0.029702
1.429000
0.000022

N2
0.372858
0.029134
1.250600
0.000019

0.580000
900.000000

0.008100
1260.874800

0.013000
0.062488

0.024000
71.040000

0.024000
1326.990336

From these data :

The total mass flowrate, m = 3558.97kg/hr
Heat rate is 104112.95 kJ/hr
From the standards, we assume the tube diameter that we want to use for the design,
also the BWG and the tube length;
Outer diameter, do (m)
BWG
Tube length, L (m)
Inlet diameter, di (m)

0.0195
10
6.096
0.0122

Based on the fouling factor that we get from literature, we assume the fouling factor for
both inside and outside of the tubes
h,di
hdo

0.000159718
5.45934E-05

For this design, the material for construction is assumed to be the stainless steel which
has the thermal conductivity of 45 W/mC
From the temperatures that we have, we find the log mean temperature difference and
then we find the correction factor from the suitable graph. From this value that we have,
we find out that the correction factor is 0.95 from the graph of one shell pass and two or
more even tube passes.
T1 (C)
T2 (C)
Tm
(C)

33.5
15
23

R 0.274509804
P 0.62962963
Based on the graph , Ft

0.95

Then by using the Ft, we find the mean temperature difference given that
DTm = LMTD Ft
From this calculation, DTm value is 21.87C
Then provisional area is being calculated which is given

Therefore, A=29.75m

6.6.2 Calculation of number of tubes

For this design, there are 80 tubes

Calculate the tube pitch and bundle diameter
K1
n1

0.319
2.142

pt (m)
0.024375
Db (m) 0.256573584
We assume the heat exchanger having fixed and U-tube floating head.
Therefore,
Bundle diameter clearance, BDC (m)
Shell diameter, Ds (m)
Baffle spacing, Bs

0.01
0.27 m
0.11 m

Then we calculate the area for cross-flow which is 0.01m

For this design, assuming that the cooling water is flowing into the shell and the main
components of the reaction flow into the tubes.
For shell-side;
Shell-side mass velocity, Gs = 173.8991 m/s
For equilateral triangle pitch arrangement, the shell equivalent diameter, de = 0.0335m
Reynolds number = 5828 (Turbulent)
Prandlt's number = 0.00722
From the chart and assume the baffle cuts to be 45%;
jh
0.055
jf
0.39
Nu
61.95
ho
0.173899098
The pressure drop in the shell is
Ps

21451.46Pa

Number of tubes per pass, Ntpp = 80

Tube-side mass velocity, Gm = 106.1619 m/s
Tube-side velocity, v = 0.4172 m/s

Density
2.32176621
Viscosity 0.000633266
Cp,mix
1.081267036
Thermal
C
0.15896931
Prandlt and Reynolds number for fluids inside the tubes are 0.004307305 and 67186
respectively.
Since the flow is turbulent, therefore the heat transfer coefficient, hi = 3129.49
By using the equation for Ui and Uo, we get;
Ui
56.41857795
Uo
17.3587232
Therefore, U = 73.78 W/mC which is in between the values of 20-300 W/mC that
we have assumed for our design problem using gases as the hot fluid and water as the
cold fluid.
Therefore our P = 25145.95Pa

7.0 CONCLUSION
As a conclusion, a proper mass and energy balances have been constructed to each of
the unit operation and linked together as a whole process. Overall and component mass
balances of every species are done on the basic in which the inlet flow rate will equal to
the outlet flow rate and there is no accumulation in the unit operation. Energy balance is
done to determine the operating condition at each unit operation and helps us to
calculate the energy utility of the process. An organized and complete Process Flow
Sheet Diagram(PFD) has been generated by using computer software, Autocad. The PFD
consists of all unit operation and auxiliary equipment that labelled in a systematic way.
Finally, different students have designed different specific unit operation involved in the
process such as fluidized bed reactor, pack column absorber, pack column stripping
column and heat exchanger. The design fulfill both chemical and mechanical
engineering requirement. To sum up the conclusion, we can say that we have achieved
all objectives in this project.
Throughout this project, our groups have learned a lot of things aside from the project
and course objectives. We start to realize the importance and application of our
previous subjects and study in our future career especially when we are required to
design a real industrial unit operation. It is not a homework or project that we can copy
from seniors or friends but each of us have to really understand the design methodology
of different type of unit operation and come out with a specific design. We have to apply
our previous knowledge such as Chemical Process Principles, Thermodynamics and
Separation to extract our equilibrium data, construct mass and energy balance, and
design a specific unit operation. Besides, our group also trained to work in a group
instead of individual. Without the cooperation and hard work from every group
members, we are sure that we cannot complete this project on time. Each of us have
been sharing knowledge and idea throughout the whole project so that we can always
learn something news from other people. Furthermore, we found out that we should not
limit our source or reference in notes given by lecturer only but we should always
broaden our knowledge from all kind of source available in the internet or library. Study
and understand of others people work sometimes can give us a better guideline on how
to do our work especially in the design of our unit operation. Hereby, we also like to
deliver our highest gratitude to our mentor Dr. Brahim on guiding us throughout the
whole project. All of us are sure that without this proper guidance, we are unable to
work on the project. Thank you.
For the coming project, our groups feel that it would be much better to have more than
one mentor because we know it is really tiring and hard for only one mentor to guide all
the students. Each of the student is designing a different unit operation and it is
sometime hard for a mentor to assist all the student due to the time constraint. So, we
feel that more mentors that have been assigned to the students might help every
student to understand or master this subject better.

LC
LT
TT
TC

Intalox
SaddleCeramic

8.0 REFERENCES
1. Felder, R.M. & Rousseau, R.W.(2005). Elementary principles of chemical
processes.(3rd Eds.). United States of America: John Wiley & Sons, Inc.
2. Perry, R.H., Green, D.W. & Maloney, J.O.(1997).Perrys Chemical Engineers
Handbook. (8theds.). United States of America: The McGraw-Hill Companies, Inc.
3. Fasullo,Sulfuric Acid: Use and Handling, at p.304 (New York: McGraw-Hill Book
Company, 1965) Copyright Chas. S. Lewis & Company,St. Louis, MO.
4. Liquid-vapor equilibrium concentration sulfuric acid-water system,vapor at
1atm.pressure,General chemical
5. C.Gerrath, Recent Developments in Chlorine Processing, Krebs & Co. Ltd Zurich,
Switzerland.
6. V. F. Giauquee, . Yi'. Hornungj., E. Kunzlearn D T. R. Rubin(1959), The
Thermodynamic Properties of Aqueous Sulfuric Acid Solutions and Hydrates
from 15 to 3OO0K, Low Temperature Laboratory, Department of Chemistry and
Chemical Engineering. University of California, Berkelev
7. Brahim, Designing a randomly packed column, Department of Chemical
Engineering, University of Malaya