CL 452 - Design Project

Spring 2019

Group 9

Nitric Acid
Final Project Report

Members
Vishal Jajodia : 15B030014
Abhishek Pawan Sharma : 150020010
Shubhangi Chuhadia : 150020072
Hrishav Ranjan : 150020074
Kshitij Chandrachoor : 150020058

Department of Chemical Engineering

Indian Institute of Technology Bombay
Contents

List of Figures v

List of Tables vi

1 Nitric Acid 1
1.1 Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Uses of Nitric Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.3 Uses of Intermediates and Byproducts . . . . . . . . . . . . . . . . . . . . 3
1.4 Grades of Nitric Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

2 Market Survey 5
2.1 World Consumption Patterns . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.2 World Production Patterns . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.3 Top Market Players . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
2.4 Technology Providers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.5 Location Selection for New Plant . . . . . . . . . . . . . . . . . . . . . . . 9

3 Production Process 11
3.1 Production Routes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3.2 Ostwald’s Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
3.2.1 Ammonia Oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . 12
3.2.2 Nitric Oxide Oxidation . . . . . . . . . . . . . . . . . . . . . . . . 12
3.2.3 Absorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
3.3 Deviations in Ostwald’s Process . . . . . . . . . . . . . . . . . . . . . . . . 14
3.3.1 Single Pressure Processes . . . . . . . . . . . . . . . . . . . . . . . 14
3.3.1.1 Medium Pressure . . . . . . . . . . . . . . . . . . . . . . 14
3.3.1.2 High Pressure . . . . . . . . . . . . . . . . . . . . . . . . 14
3.3.2 Dual Pressure Process . . . . . . . . . . . . . . . . . . . . . . . . . 15
3.4 Selection of Final Process . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

4 Industrial Visit 18
4.1 Process Highlights . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
4.1.1 Ammonia . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
4.1.2 Ammonia Filters . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
4.1.3 Air Filters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
4.1.4 Ammonia - Air Mixer . . . . . . . . . . . . . . . . . . . . . . . . . 19
4.1.5 Turbine Shaft . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
4.1.6 Reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20

ii
 4.1.7 Boiler . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
4.1.8 Cooler Condenser . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
4.1.9 Absorption Column . . . . . . . . . . . . . . . . . . . . . . . . . . 21
4.2 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21

5 Process Flow Diagram 22

5.1 Process Flow Diagram . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
5.2 Process Explanation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
5.3 Process Heat Integration . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25

6 Mass Balance 29
6.1 Sample Calculations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
6.1.1 Reactor - R101 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
6.1.2 Heat Exchangers and Cooler Condenser . . . . . . . . . . . . . . . 31
6.1.3 Absorption Column and Cooler Condenser . . . . . . . . . . . . . 32
6.2 Final Mass Balance Table . . . . . . . . . . . . . . . . . . . . . . . . . . . 32

7 DWSIM Flowsheet Simulation 34

7.1 Kinetics and Specification used in DWSIM . . . . . . . . . . . . . . . . . . 34
7.1.1 Ammonia Oxidation . . . . . . . . . . . . . . . . . . . . . . . . . . 34
7.1.2 Nitric Oxide Oxidation . . . . . . . . . . . . . . . . . . . . . . . . 35
7.1.3 Absorption Column . . . . . . . . . . . . . . . . . . . . . . . . . . 36
7.2 Comparisons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
7.2.1 Ammonia Reactor . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
7.2.2 Heat Exchangers . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
7.2.3 Absorption Column . . . . . . . . . . . . . . . . . . . . . . . . . . 38

8 Sensitivity Analysis 39
8.1 Reactor Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
8.2 Heat Exchanger simulated as PFR . . . . . . . . . . . . . . . . . . . . . . 40
8.3 Absorption Column Analysis . . . . . . . . . . . . . . . . . . . . . . . . . 41

9 Equipment Sizing and Costing 43

9.1 Ammonia Oxidation Reactor . . . . . . . . . . . . . . . . . . . . . . . . . 43
9.1.1 Diameter Calculation . . . . . . . . . . . . . . . . . . . . . . . . . 44
9.1.2 Catalyst Costs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
9.1.3 Burner Head Calculation . . . . . . . . . . . . . . . . . . . . . . . 45
9.2 Storage Tanks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
9.3 Compressors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
9.4 Pumps . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
9.5 Heat Exchangers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
9.6 Columns . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
9.6.1 Shell Calculations . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
9.6.2 Tray Calculations . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53

10 Plant Economics 55
10.1 Major Equipment Costing . . . . . . . . . . . . . . . . . . . . . . . . . . . 55
10.2 Capital Investment Estimation . . . . . . . . . . . . . . . . . . . . . . . . 56

iii
 10.3 Raw Material Cost . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
10.4 Revenue Calculation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
10.5 Total Product Cost . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
10.6 Payback Period . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58

11 Detailed Design - Absorption Column 61

11.1 Mathematical Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
11.2 Tray Selection and Specifications . . . . . . . . . . . . . . . . . . . . . . . 65
11.2.1 Weeping Check . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
11.2.2 Plate Pressure Drop . . . . . . . . . . . . . . . . . . . . . . . . . . 66
11.2.3 Perforated Area and Hole Pitch . . . . . . . . . . . . . . . . . . . . 66
11.2.4 Number of Holes . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
11.3 Head Selection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
11.4 Tower Thickness . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69

12 Environmental Impact 71
12.1 Tail Gas Composition and Emission Limits . . . . . . . . . . . . . . . . . 71
12.2 Abatement Technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
12.3 Tail Gas Post Abatement . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
12.4 Revised Plant Economics . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
12.4.1 Reactor Unit Cost . . . . . . . . . . . . . . . . . . . . . . . . . . . 74
12.4.2 Additional Raw Material Costs . . . . . . . . . . . . . . . . . . . . 74
12.4.3 Additional Revenue Calculation . . . . . . . . . . . . . . . . . . . . 75
12.4.3.1 No CER Revenue . . . . . . . . . . . . . . . . . . . . . . 75
12.4.3.2 With CER Revenue . . . . . . . . . . . . . . . . . . . . . 76

A Final Process Flow Diagram 77

B MATLAB Code for the Mathematical Model for NOX Absorption 79

C Detailed Drawing of Absorption Column 82

References 84

iv
List of Figures

1.1 Uses of Nitric Acid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2

2.1 World Nitric Acid Consumption . . . . . . . . . . . . . . . . . . . . . . . . 6

2.2 World Nitric Acid Production . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.3 Nitric Acid Top Market Players . . . . . . . . . . . . . . . . . . . . . . . . 8

3.1 Block Diagram of Ostwald’s Process . . . . . . . . . . . . . . . . . . . . . 13

4.1 Ammonia Flow through Ceramic Filters . . . . . . . . . . . . . . . . . . . 19

4.2 DFPCL Turbine Shaft Structure . . . . . . . . . . . . . . . . . . . . . . . 20
4.3 Nitric Acid Cooler Condenser . . . . . . . . . . . . . . . . . . . . . . . . . 21

5.1 Heat Exchanger Network . . . . . . . . . . . . . . . . . . . . . . . . . . . 27

5.2 Process Flow Diagram for Dual Pressure Nitric Acid Process . . . . . . . 28

7.1 DWSIM Flowsheet - Ammonia Oxidation . . . . . . . . . . . . . . . . . . 35

7.2 DWSIM Flowsheet - NO Oxidation and Heat Exchanger Network . . . . . 36
7.3 DWSIM Flowsheet - Reactive Absorption Column Modelling . . . . . . . 37

8.1 Sensitivity Analysis for Reactor . . . . . . . . . . . . . . . . . . . . . . . . 39

8.2 Sensitivity Analysis for Heat Exchanger . . . . . . . . . . . . . . . . . . . 40
8.3 Sensitivity Analysis for Absorption Column - 1 . . . . . . . . . . . . . . . 41
8.4 Sensitivity Analysis for Absorption Column - 2 . . . . . . . . . . . . . . . 41

10.1 Estimated Cash flow from Plant Operation . . . . . . . . . . . . . . . . . 60

11.1 Sieve Tray Perforated Area with Downcomer . . . . . . . . . . . . . . . . 68

11.2 Sieve Tray Cooling Coils . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68

12.1 EnviNOX R Process Variant - 2 . . . . . . . . . . . . . . . . . . . . . . . . 73

v
List of Tables

1.1 Nitric Acid Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

2.1 World Nitric Acid Production . . . . . . . . . . . . . . . . . . . . . . . . . 6

2.2 Big Players in Global Market . . . . . . . . . . . . . . . . . . . . . . . . . 8
2.3 Big Players in Domestic Market . . . . . . . . . . . . . . . . . . . . . . . . 8

3.1 Temperature and Pressure Dependence of Ostwald’s Process . . . . . . . . 14

5.1 Utility Data after Heat Integration . . . . . . . . . . . . . . . . . . . . . . 26

6.1 Reactor Balance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30

6.2 Heat Exchanger Balance . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
6.3 Absorption Column and Cooler Condenser Balance . . . . . . . . . . . . . 32
6.4 Final Mass Balance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33

7.1 Mass Balance Comparison for Reactor . . . . . . . . . . . . . . . . . . . . 37

7.2 Mass Balance Comparison for Heat Exchanger network . . . . . . . . . . . 38
7.3 Mass Balance Comparison for Absorption Column . . . . . . . . . . . . . 38

9.1 Catalyst Costs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45

9.2 Burner Head Design Parameters . . . . . . . . . . . . . . . . . . . . . . . 45
9.3 Burner Head Costing Parameters . . . . . . . . . . . . . . . . . . . . . . . 45
9.4 Nitric Acid Storage Tank Costing . . . . . . . . . . . . . . . . . . . . . . . 46
9.5 Compressor Power Calculation . . . . . . . . . . . . . . . . . . . . . . . . 47
9.6 Costing of Multi Stage Compressors with Turbines . . . . . . . . . . . . . 48
9.7 Pump Costing Factors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
9.8 Pump Factors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
9.9 Costing of Centrifugal Pumps . . . . . . . . . . . . . . . . . . . . . . . . . 50
9.10 Operating Parameters and Costing of Heat Exchangers . . . . . . . . . . . 51
9.11 Column Parameters and Costing . . . . . . . . . . . . . . . . . . . . . . . 53
9.12 Sieve Tray Costing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
9.13 Total Purchased Costs for Columns . . . . . . . . . . . . . . . . . . . . . . 54

10.1 Total Purchased Equipment Cost . . . . . . . . . . . . . . . . . . . . . . . 55

10.2 Total Capital Investment Estimation . . . . . . . . . . . . . . . . . . . . . 56
10.3 Total Raw Material Cost Calculation . . . . . . . . . . . . . . . . . . . . . 57
10.4 Total Revenue Calculation . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
10.5 Total Product Cost Estimation . . . . . . . . . . . . . . . . . . . . . . . . 58
10.6 Cash Flow from Plant production . . . . . . . . . . . . . . . . . . . . . . . 59
10.7 Plant Economics Comparison with recently setup plant . . . . . . . . . . 60

vi
11.1 Mathematical Model Results . . . . . . . . . . . . . . . . . . . . . . . . . 63
11.2 Tray Selection Parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
11.3 Final Tray Specifications . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
11.4 Final Column Specifications . . . . . . . . . . . . . . . . . . . . . . . . . . 70

12.1 Composition of Tail Gas leaving Absorption Column . . . . . . . . . . . . 71

vii
Chapter 1

Nitric Acid

Nitric acid (HNO3 ) is a highly corrosive mineral acid and powerful oxidizing agent. It
occurs in nature only in the form of nitrate salts. The pure compound is a colorless
liquid, but tends to acquire a yellow cast due to the accumulation of oxides of nitrogen if
stored for long. Most commercially available nitric acid has a concentration of 55-70%,
being centrally used in production of nitrogen fertilisers, nylon and explosives.

1.1 Properties

Property Name Property Value

Molecular Weight 63.012 g/mol
Colour Colourless
Boiling pt 83◦ C
Density 1.512 g/cm3
Azeotropic composition 68% w/w (BP = 120.5◦ C)
Thermal conductivity (20◦ C) 0.343 W/m.K
Standard enthalpy of formation 2.7474 J/g (Liquid); 2.1258 J/g (Gas)
Heat of vaporization (20◦ C) 626.3 J/g
Specific heat (20◦ C) 1.7481 J/g.K

Table 1.1: Nitric Acid Properties

1
Nitric Acid 2

The tabulated data above lists some of its chemical and physical properties, acquired
from PubChem1 . Nitric acid is a nitogen oxoacid, with a nitrogen atom bonded to a
hydroxyl group and by equivalent resonating double bonds to the remaining two oxygen
atoms, giving the N-atom a +5 oxidation state. This can be seen in the HNO3 structure
shown below :

H O

O N+

O−

1.2 Uses of Nitric Acid

Figure 1.1: Uses of Nitric Acid, recreated from Thyssenkrupp Nitric Acid Book [1]

Nitric acid is widely used as an intermediate and its demand majorly depends on the
demand of the end product for which it is used as a raw material. About 90% of nitric
acid is used for on-site consumption and only 10% accounts for retail market. Nitric
Acid is used for following purposes :
1
https://pubchem.ncbi.nlm.nih.gov/compound/nitric_acid#section=
Chemical-and-Physical-Properties
Nitric Acid 3

• About 80% of the world production is used as raw material in the production of
Ammonium Nitrate in the fertiliser industry

• Used as a raw material in the production of Adipic acid, which is further employed
in manufacturing Nylon-6,6 resins and fibres - widely used in automotive industry

• Used as a raw material for the production of Nitrobenzene - a precursor to Aniline,

which finds widespread use in the pharmaceutical industry

• Used in manufacturing explosives in mining/construction industry

• Used in manufacturing Polyurethane and Polyamide and also as an oxidiser in

liquid fueled rockets

1.3 Uses of Intermediates and Byproducts

• NO - Nitric oxide is used together with a breathing machine (ventilator) to treat

respiratory failure in premature babies. In the human body, nitric oxide expands
the blood vessels, increasing blood flow and decreasing plaque growth and blood
clotting.

• NO2 - Nitrogen Dioxide is used as an oxidising agent in certain oxidation reactions,

as an inhibitor to prevent polymerization of acrylates during distillation, as a
nitrating agent for organic compounds, as a rocket fuel, as a flour bleaching agent
and in increasing the wet strength of paper.

• N2 O - Nitrous oxide has significant medical uses, especially in surgery and den-
tistry, for its anaesthetic and pain reducing effects. Its name ”laughing gas” is due
to the euphoric effects upon inhaling it, a property that has led to its recreational
use as a dissociative anaesthetic.

Even though these byproducts find significant uses multiple sectors of industry, they
are major pollutants when produced in large amounts, with NO and NO2 being the
main causes for acid rains and air pollution and N2 O being a major greenhouse gas,
contributing to the depletion of Ozone layer and trapping of heat within the atmosphere,
and hence, require to be eliminated as per Government of India norms before being
expanded into air.
Nitric Acid 4

1.4 Grades of Nitric Acid

There are two major commercially available grades of Nitric Acid :

• Weak Nitric Acid (WNA) - Nitric acid having a concentration of 55-70%

wt.HNO3 . WNA is widely used in the fertiliser industry as the starting raw ma-
terial for Ammonium Nitrate.

• Concentrated Nitric Acid (CNA) - Nitric acid having a concentration of

>90% wt.HNO3 . CNA is widely used as a nitration agent in manufacturing explo-
sives, nitroalkanes and nitroaromatics and also as an oxidising agent in multiple
industries and laboratories.
Chapter 2

Market Survey

Due to the rapidly increasing population and reduced availability of land for irrigation,
there is an increasing demand for fertilisers. The use of nitric acid as an intermediate
in the production of ammonium nitrate is a key factor, boosting the production as well
as the consumption of HNO3 . Growing automotive industry drives concentrated nitric
acid market as it is utilized in manufacturing of light weight and strong body parts of
vehicles. Rising demand for synthetic rubbers, elastomers and polyurethane foams in the
automotive industry is anticipated to drive the product demand as well. All the findings
of this section were made after referring Nitric Acid Market Research reports provided
by Research and Markets1 [2], Grand View Research2 [3] and IHS Chemical Economics
Handbook3 [4].

2.1 World Consumption Patterns

The largest market for nitric acid is the production of ammonium nitrate (AN) and
calcium ammonium nitrate (CAN), accounting for almost 77% of the total world con-
sumption of nitric acid in 2016. World nitric acid consumption has exhibited a steady
upward trend since 2000, with average annual growth rates of 2.0% during 2000–16.
1
https://www.researchandmarkets.com/research/qsn6h4/global_nitric
2
https://www.grandviewresearch.com/industry-analysis/nitric-acid-market
3
https://ihsmarkit.com/products/nitric-acid-chemical-economics-handbook.html

5
Market Survey 6

Figure 2.1: World Nitric Acid Consumption, recreated from [4]

Europe, United States and China account for more than 80% of global demand. Europe
and China are the largest consumers of nitric acid and accounted for around 60% of the
global consumption. Since 2000, the largest increase in consumption has occurred in
China, at an average annual growth rate of 7.3%.

The presence of large agricultural and industrial market in Asia–Pacific is a key fac-
tor responsible for the high growth of the global nitric acid market. Also, the stringent
regulations in regions like North America and Europe regarding the use of ammonium
nitrate based fertilisers are likely to shift the demand to countries in the Asia–Pacific.

2.2 World Production Patterns

Year Nitric Acid Produced (tons) Increase (tons)

2010 7,419,644 –––
2011 7,642,233 222,589
2012 7,871,500 229,267
2013 8,107,645 236,145
2014 8,350,874 243,229
2015 8,601,401 250,526
2016 8,859,443 258,042
2017 9,125,226 265,783

Table 2.1: World Nitric Acid Production

Market Survey 7

Figure 2.2: World Nitric Acid Production, recreated from [2]

Europe and North America account for more than 80% of the global production.

In North America, the United States dominated the market with a revenue share of
69% in 2014 and it is estimated to continue the trend over the forecast period. Robust
manufacturing base of chemical, electronics, and automotive industries in the U.S. is
anticipated to supplement the growth of the market in the region.

In Western Europe, Germany represented 13% of the overall revenue in 2014. Lead-
ing chemical companies such as BASF, Bayer and Henkel have their established man-
ufacturing units intended for the production of application–specific bulk chemicals and
specialty polymers in Germany. Aforementioned factors are influencing the growth of
the market in Western Europe positively. Presence of advanced fertilizer manufacturing
facilities in Russia along with abundant availability of raw materials such as ammonia
is projected to be a favorable factor for the market.

Ammonia is the key raw material used in the manufacturing of nitric acid. Ammo-
nia production is concentrated mainly in the U.S., China, Eastern Europe and Middle
East because of the availability of large natural gas reserves in these reigons.
Market Survey 8

2.3 Top Market Players

Figure 2.3: Nitric Acid Top Market Players, recreated with data from [2]

Table 2.2: Big Players in Global Market

BASF SE Germany
Shandong Fengyang China
Agrium Inc. Canada
Apache Nitrogen Products, Inc. USA
Yara International Norway
OCI NV Netherlands
CF Industries Holdings, Inc. USA
Dow Chemicals USA
Potash Corp of Saskatchewan Canada
LSB Industries Inc. USA

Table 2.3: Big Players in Domestic Market

Gujarat Narmada Valley Fertilizers Bharuch, Gujarat
Company Ltd.
Vijay Gas Industry Pvt. Ltd Mumbai, Maharashtra
Rashtriya Chemicals and Fertilizers Raigad & Mumbai, Maharashtra
Ltd.
Deepak Fertilizers and Petrochem- Taloja, Maharashtra; Srikakulam,
icals Corporation Ltd. A.P.; Panipat, Haryana; Dahej,
Gujarat
Surya Fine Chemicals Boisar & Palghar, Maharashtra
Market Survey 9

2.4 Technology Providers

• Weatherly, a company of Chematur Engineering Group of Sweden

• ESPINDESA, a company of Técnicas Reunidas of Spain

• Borealis of Austria

• Uhde GmbH (now ThyssenKrupp Industrial Solutions) of Germany

• MECS Technology of USA

• KBR of USA

• Technip of France

2.5 Location Selection for New Plant

Option 1 : Ukraine

• Cheaper raw material availability (Ammonia - $250-$300/ton)

• High demand for Nitric acid in neighboring countries (Nitric Acid - $300-$400/ton)

• Ease in exporting products and materials (Bordering Black Sea and close to mul-
tiple fertiliser conglomerates)

• Europe being the largest consumer of Nitric Acid provides proximity to desired
market

Option 2 : India

• Cheaper Labour costs

• Vast import and export opportunities(surrounded by highly populated nations)

• High local demand and Lax environmental norms

• Large agricultural markets of South East Asia provide huge selling outlets for nitric
acid products like Ammonium Nitrate fertilisers

• Stringent regulations on Nitrate fertilisers in North America and Europe can cause
a shift in the production and selling of these product in and around the Asia Pacific
Market Survey 10

Based on the above mentioned factors, and factors mentioned below, the final location
for the Nitric Acid plant was selected to be Hazira, Gujarat, India

Reasons for selecting Hazira, Gujarat :

• Raw Material Advantage : close to largest Ammonia plant in India - KRIBHCO

• Proximity to Hazira Port and nearby product procurers

• Well established industrial area with great connectivity to the rest of world
Chapter 3

Production Process

This chapter provides details about various production methods for nitric acid, from
laboratory methods to the widely used commercial processes, including their advantages
and disadvantages, and finally ending with the determination of the right process for
the plant and its capacity.

3.1 Production Routes

• From Chile Saltpeter (NaNO3 ) :

N aN O3 + H2 SO4 → N aHSO4 + HN O3

• From Electric Oxidation of Air :

N2 + O2 → 2N O

2N O + O2 → 2N O2

3N O2 + H2 O → 2HN O3 + N O

• From thermal decomposition of Copper(II) Nitrate :

2Cu(N O3 )2 (s) → 2CuO(s) + 4N O2 (g) + O2 (g)

All these processes have become obsolete and the only industry used process is the
Catalytic Oxidation of Ammonia by the Ostwald’s Process and its variants.

11
Production Process 12

3.2 Ostwald’s Process

Referring to Moulijn et. al. [5], the Ostwald’s Process involves three steps –(i) Ammonia
Oxidation (ii) Nitric Oxide Oxidation (iii)Nitrogen Dioxide Oxidation

3.2.1 Ammonia Oxidation

4N H3 (g) + 5O2 (g) → 4N O(g) + 6H2 O(g), ∆H = −905kJ/mol

A 1:9 ammonia/air mixture by volume is oxidized at a temperature of 750◦ C to 900◦ C

as it passes through a catalytic convertor.
Catalyst: 90% platinum - 10% rhodium gauze constructed from squares of fine wire.
Yield: Under these conditions the oxidation of ammonia to nitric oxide (NO) proceeds
in an exothermic reaction with a range of 93 to 98 percent yield.
Side Reactions:

4N H3 (g) + 4O2 (g) → 2N2 O(g) + 6H2 O(g), ∆H = −1102kJ/mol

4N H3 (g) + 3O2 (g) → 2N2 (g) + 6H2 O(g), ∆H = −1261kJ/mol

Oxidation temperatures can vary from 750◦ C to 900◦ C. Higher catalyst temperatures
increase reaction selectivity toward NOs production. Lower catalyst temperatures tend
to be more selective toward less useful products: nitrogen (N2 ) and nitrous oxide (N2 O).
Nitric oxide is considered to be a criteria pollutant and nitrous oxide is known to be a
greenhouse gas.
High temperature and low pressure make the reaction more selective towards de-
sired product (NO gas); also owing to the high spontaneity of the reactions, catalytic
bed reactor of residence time 10−4 to 10−3 seconds is used.

3.2.2 Nitric Oxide Oxidation

The process stream is passed through a series of heat exchangers and cooler–condensers
and cooled to 50◦ C or less at pressures up to 4 barg. The nitric oxide reacts non
catalytically with residual oxygen to form nitrogen dioxide (NO2 )

2N O(g) + O2 (g) → 2N O2 (g), ∆H = −114kJ/mol

Production Process 13

This slow, homogeneous reaction is highly temperature and pressure dependent. Oper-
ating at low temperatures and high pressures promotes maximum production of NO2
within a minimum reaction time.

3.2.3 Absorption

The oxidised gas mixture is fed into the bottom of the absorption tower, while liquid
acid condensate is added at a higher point. Deionized process water enters the top of
the column. Both liquids flow counter–current to the NOX gas mixture. Oxidation takes
place in the free space between the trays, while absorption occurs on the trays. The
absorption trays used are sieve trays.

3N O2 (g) + H2 O(l) → 2HN O3 (aq.) + N O(g), ∆H = −75kJ/mol

A secondary air stream is introduced into the column to re-oxidize the NO that is
formed in this reaction. This secondary air also removes NOX from the product acid.
An aqueous solution of 55 to 65 percent (typically) nitric acid is withdrawn from the
bottom of the tower. The acid concentration depends upon the temperature, pressure,
number of absorption stages, and concentration of nitrogen oxides entering the absorber.

Figure 3.1: Block Diagram of Ostwald’s Process

Production Process 14

3.3 Deviations in Ostwald’s Process

Referring to Moulijn et. al. [5], we found out that the principal design variables for the
ammonia oxidation and subsequent stages of the plant are temperature, pressure and
gas flow rate, and their effects on the process efficiency is tabulated below:

Process Change NH3 Oxidation NO Oxidation Absorption

Temperature Increase Higher Yield Lower Yield Reduced absorp-
tion
Pressure Increase Oxidation rate re- Higher Yield Improved absorp-
duced. Amount of tion
NH3 oxidised per unit
time increases
Flow Rate Increase Optimum temp. in- Higher yield Minor improve-
creases. Higher Yield ments

Table 3.1: Temperature and Pressure Dependence of Ostwald’s Process

According to Thiemann et. al. [6] and Thyssenkrupp Nitric Acid Book [1], classification
of plants is done on the basis of pressure in the oxidation and absorption stages:

3.3.1 Single Pressure Processes

3.3.1.1 Medium Pressure

This type of nitric acid plant operates at around 4–5 bars abs. It can produce up to
700 tonnes/day using a single combustion and a single absorption tower and around
1000 tonnes/day by adding another absorption tower. Using this pressure enhances the
oxidation step (NO to NO2 ), but reduces the productivity of the final absorption stage.

3.3.1.2 High Pressure

Pressure of around 8–12 bars abs is used. This high pressure forces the nitrogen dioxide
gas into water. And thus, a single absorption tower is sufficient to produce 1000 ton-
nes/day of nitric acid. The higher pressure means that other equipment like the burner
Production Process 15

unit, piping can be made smaller so the plant occupies less space, making the initial
capital investment less.

3.3.2 Dual Pressure Process

• Low to Medium dual pressure: 1–2/ 4–5 bars abs

• Medium to High dual pressure: 4–5/ 8–12 bars abs

Lower pressure for ammonia oxidation and higher pressure for absorption is favourable.
The dual pressure plant uses two different pressures, a lower pressure for the oxidation
step and higher pressure to optimize the absorption. This type of plant can produce up
to 1500 tonnes/day of nitric acid using single combustion and absorption unit. Lower
pressure for the oxidation unit also reduces the catalyst cost.

3.4 Selection of Final Process

The points considered while finalising the actual process to be utilised in the plant are:

• Variable Costs

• Capacity

• Catalyst Life

• Catalyst Performance and Loss

• Environmental Impact

• Absorption Column Efficiency

• Desired Nitric Acid Concentration

• Electric Power

In accordance with the above mentioned points, the following comparisons1 are docu-
mented and are also an industry–wide practice:
1
All comparisons are per tonne Nitric Acid (100%)
Production Process 16

• The dual pressure process provides larger capacities (upto 1600 tpd in single train
configuration) with relatively lower variable costs, when compared to the mono
pressure processes(upto 900 tpd for high pressure, upto 700 tpd for medium pres-
sure - in single train configuration), which require larger variable costs.

• The dual pressure process was designed to accommodate more stringent environ-
mental pollution control requirements, namely to reduce the emissions of NOX
gases into the atmosphere. The process has inherent abilities to reduce the outgo-
ing tail gas to a composition well below the required environmental norms. This
reduction in composition is a result of an increased absorption column efficiency
due to the increased absorption column pressure incorporated in the dual pressure
process.

• Due to a lower load on the burner, the dual pressure process also provides with a
longer operation time for a given bundle of catalyst gauzes(> 6–8 months), when
compared to the other available processes(upto 6 months). This effect can be
seen directly on the total catalyst losses for dual pressure process (0.03g/t of nitric
acid produced) when compared to the mono pressure processes (0.04g/t nitric acid
produced for medium pressure process and 0.08g/t nitric acid produced for high
pressure processes respectively)

• All processes can easily provide the required nitric acid concentration (≈ 60% wt)

• When comparing all the alternatives, the dual pressure process requires the least
amount of electric power per ton nitric acid produced (8.5 kWh), followed by
medium pressure (9.0 kWh) and high pressure (13.5 kWh)

Keeping in mind the desired production from our plant, the final route for the produc-
tion of nitric was chosen to be the Dual Pressure Process, with medium pressure
ammonia oxidation over Pt–Rh catalyst and high pressure absorption operations.

Licensor - Uhde GmbH, Germany

Existing plants using this route:

• Abu Qir Fertilisers and Chemical Ind. Co., Abu Qir, Egypt –Capacity –1850TPD

• Borealis AG, Linz, Austria –Capacity –1000TPD

Production Process 17

(As an industry standard, plant capacities are displayed in terms of 100% wt nitric acid)

Capacity of Proposed plant:

With reference to average plant capacities using dual pressure process and keeping in
mind the demand for nitric acid in India, the final plant capacity has been decided to
be kept at 1500TPD of 62% wt nitric acid (942TPD in terms of 100% wt)
Chapter 4

Industrial Visit

In order to gain a better understanding of the selected process and to aid selection
of parameters and equipment, a visit to Deepak Fertilizers and Petrochemical Corp.
Ltd.(DFPCL) [7] was made on February 6, 2019.
Total Nitric Acid Capacity: 1400TPD
4 nitric acid plants:
2 mono high pressure plants (300TPD each, set up in 1996
1 mono medium pressure plant (350TPD, set up in 2000)
1 dual pressure plant (450TPD, set up in 1975, Denmark, recommissioned in 2010, India)

The weak nitric acid (59.2% wt) produced here is used further for ammonium nitrate
production and concentrated nitric acid (98.5%wt) is sold separately. Since the dual
pressure plant is recommissioned, it has a few added features to adjust to the tempera-
ture and pressure in India. For example, the compressors used are designed for a lower
air temperature (Denmark) whereas the ambient air temperature in India is high. Hence,
air chillers are added to reduce the temperature of the air to 20◦ C before compression.

4.1 Process Highlights

4.1.1 Ammonia

Deepak Fertilisers has a separate plant for ammonia production which usually meets the
nitric acid requirement. An alternate of sourcing ammonia externally during off days is
18
Industrial Visit 19

also in place. The ammonia obtained is stored in a cylindrical storage refrigerated tank
at -33◦ C and 1 atm pressure.

4.1.2 Ammonia Filters

Ceramic tubes are used to filter oil, water and other impurities from ammonia. The
ammonia feed enters radially, is filtered and exits through the axis.

Figure 4.1: Ammonia Flow through Ceramic Filters

4.1.3 Air Filters

The air is compressed to 5 bar using a centrifugal compressor. Primary and Secondary
Filters are used to filter out particulate matter before compression. These filters are
made of Stainless Steel and present in huge numbers, incorporated with the cooling
network inside the filter rack.

4.1.4 Ammonia - Air Mixer

Mixer used in the industry is a Stainless Steel Static Mixer, where both the gas streams
are intermixed, entering perpendicular to each other.

4.1.5 Turbine Shaft

A single steam turbine is used to rotate a shaft which is connected to a series of compres-
sors and expanders. HP steam is used to rotate the turbine at 7000 RPM. The turbine
Industrial Visit 20

shaft is used to rotate a centrifugal compressor, which compresses air from atmospheric
pressure to 5 bar abs pressure. The second equipment on this shaft is an expander; it
reduces the pressure of the tail gas from approximately 12 bar to 1 atm. A gear (1:14)
is used after that to increase the rotations per minute for the NOX compressor. The
energy from steam and tail gas is efficiently used to run the compressor shafts.

Figure 4.2: Turbine Shaft Structure, as seen in the DFPCL Dual Pressure Plant

4.1.6 Reactor

A shallow bed reactor with 8 gauzes of 95-5 Pt-Rh is used. The reaction is highly
exothermic and takes place at 890◦ C. For the start-up of the process, hydrogen gas
is burned to raise the temperature of the gauzes (around 8 cylinders of hydrogen are
kept in the inventory (4 for main use + 4 for extra backup)). After the reaction starts,
the heat of the reaction is sufficient to maintain that temperature. 96% of ammonia
is converted in a single pass. Catchment gauzes of Palladium are provided to capture
catalyst chipped off with outgoing stream.

4.1.7 Boiler

The product stream leaving from the reactor exits at 890◦ C. This steam is to be cooled
before adding to the absorption column. And therefore, a series of heat exchangers and
cooler condensers are added. A waste heat boiler is attached just below the reactor
setup, with hot water flowing through the tube side. In the boiler, the temperature of
the process stream is reduced from 890◦ C to 410◦ C. High pressure steam is produced
while cooling the process stream, which is used to run the steam turbine.

4.1.8 Cooler Condenser

There were three cooler condensers used instead of the conventional two to reduce the
load on condensers.
Industrial Visit 21

Figure 4.3: Nitric Acid Cooler Condenser Structure, provided by DFPCL [7]

4.1.9 Absorption Column

A sieve tray counter-current absorption column (42 m in height) absorbs incoming NOX
into process water stream to form 59% w/w Nitric Acid as bottom product. NO2
absorption in water occurs on the tray whereas NO oxidation to NO2 occurs between
the trays. Cooling water coils at each stage are used to absorb the heat released by
reactions.

4.2 Conclusion

The process studied from literature and the one being used in the plant was very sim-
ilar. Doubts regarding the type of equipment used, exact conversions and temperature
pressure conditions were solved by this visit. The size of the DFPCL Dual Pressure
Plant was comparatively low and with reference to findings from the visit, changes were
made to scale up the plant capacity for our new plant.

We would like to thank the Overall Supervisors, Nitric Acid Process Head and the Nitric
Acid Dual Pressure Plant Staff of the DFPCL Taloja Plant for providing us with this
opportunity to visit their plant, spend time within the plant premises and for providing
us valuable information and data regarding the Dual Pressure Process.
Chapter 5

Process Flow Diagram

This chapter showcases the Process Flow Diagram (PFD) for the Dual Pressure Nitric
Acid Process. The PFD was made with inputs from Moulijn et. al. [5], Thiemann et.
al. [6] and DFPCL Staff [7]. The PFD was drawn using an online flowsheet drawing
software Draw.io1 .

5.1 Process Flow Diagram

The final PFD for our Dual Pressure Nitric Acid Process is available in Appendix A

5.2 Process Explanation

• Air (stream-1) is pumped into the plant at ambient conditions (1 atm, 35◦ C),
entirely by the suction force provided by the centrifugal compressor, C101. The
Air is filtered using primary and secondary Air Filters in F101 and fed to the
compressor (stream-1A).

• The compressor C101 is used to increase the pressure of the air feed to 5 bar, also
causing an increase in the temperature to 240-250◦ C. Stream-1B is split into 2
parts, 85% going into the reaction mixture (Primary Air, stream-1C) and the rest
(Secondary Air, stream-1D) is utilised in the bleaching column, B101.
1
https://www.draw.io/

22
Process Flow Diagram 23

• Liquid Ammonia from storage is pumped into the plant at -33◦ C and 19 bar, into
Evaporator E101 by a Centrifugal Pump, numbered stream-2. In the Evaporator,
Ammonia is converted to vapor and further superheated to 70◦ C with the help of
LP Steam (4-5 bar, 150◦ C) in the upper section of Evaporator E101.

• Ammonia Filter, F102 is utilised to filter the superheated Ammonia vapor (stream-
2A) of the small amounts of impurities inherent to the Ammonia feed (oils, chlorine,
etc.).

• The superheated ammonia vapor and the compressed air stream are mixed in a
static mixer, giving us stream-3, at 5 bar, 220-230◦ C. It is ensured that Ammonia
to Air ratio is kept 1:9 by volume.

• Stream-3 is fed into the reactor, R101, which is a shallow bed reactor, with around
8-10 catalyst gauzes, made up of 90% Pt and 10% Rh. Hydrogen gas is utilised
to heat up the gauzes to the required temperature at startup; once the reaction
starts, the heat of the reaction is sufficient to sustain the reaction.

• The catalyst is highly selective, giving a conversion of 96% for Ammonia into
Nitric Oxide, with stream-4 exiting at a temperature of 890◦ C, consisting mainly
of Nitrogen and Oxygen from Air feed and Nitric Oxide formed via Ammonia
oxidation.

• The high heat of reaction is used to make steam and heat other streams throughout
the plant. Shell and Tube Heat Exchanger, HE102 is used to heat the tail gas
(stream-10) coming from Absorption Column to facilitate the abatement process
(tail gas is passed through an expander where it drives the compressor C102 shaft),
and HE103 is used as a waste heat boiler, which results in the temperature of
stream-5 to drop to 185◦ C.

• This decrease in the temperature leads to the oxidation of Nitric Oxide to Nitrogen
Dioxide (stream-6), with the conversion of the reaction increasing with a decrease
in the temperature.

• Cooler Condenser-1 (HE104), is used to cool the stream further, condense water
and nitric acid and separate them out for further processing. The temperature
of the outlet streams (7 & 8) is around 50◦ C. This drop in temperature allows
Process Flow Diagram 24

Nitric Oxide to oxidise to Nitrogen Dioxide at a much higher conversion rate when
compared to the previous two heat exchangers (HE102 & HE103).

• As Nitrogen Dioxide is produced, with the drop in temperature and elevated pres-
sures, some of it gets absorbed into the condensed Water formed in reactor (R101).
Once absorbed, Nitrogen Dioxide combines with Water to form Nitric Acid and
Nitric Oxide, which further gets oxidised to Nitrogen Dioxide, which again forms
Nitric acid and so on.

• The Nitric Acid solution in the condensate of the Cooler Condenser-1 (HE104),
with a concentration of about 35-40% wt Nitric Acid by weight, is then pumped
(stream-7) to the Absorption Column (A101) to increase the Nitric Acid concen-
tration in the solution.

• The vapor outlet of HE104, stream-8, mainly consisting of NOX gases, is passed
through the NOX Compressor, C102, elevating the pressure of the stream to 12
bar and the temperature to around 165◦ C.

• C102 outlet, stream 8A, is the fed to Cooler Condenser-2 (HE105), where process
similar to that in Cooler Condenser-1 (HE104) occurs, providing us with more
weak Nitric Acid condensate, which is mixed with HE104 condensate and pumped
to the Absorption Column. Stream-9 coming out of HE105 is also fed to the
Absorption Column (A101).

• The Absorption Column (A101), has 35-40 stages, with the NOX gases (stream-9)
fed at the bottom-most stage, process water (stream-12) fed at the top-most stage,
acid condensate from the Cooler Condensers (stream-7) fed to an intermediate
stage (stage 24) and cooling water coils at every stage throughout the column to
maintain the column at a reduced temperature.

• Since the Absorption Column is operated at an elevated pressure, absorption effi-

ciency is increased, which results in fewer NOX emissions.

• Inside the column, Nitric Oxide oxidation to Nitrogen Dioxide occurs between
stages in the vapor phase, and absorption of Nitrogen Dioxide into water and the
formation of Nitric Acid from the absorbed Nitrogen Dioxide occurs in the liquid
phase on the sieve trays of the column.
Process Flow Diagram 25

• Top outlet of the column is called Tail Gas (stream-10), with NOX concentration
in the order of 2000ppmv. Stream-10 is then preheated in HE106 using secondary
air (stream-1D) and further heated HE102 using stream-4 and sent to the NOX
abatement process where it is expanded to drive the compressor C102 shaft and
then vent into the air.

• Bottom outlet of the column (stream-11) is called Red Fuming Nitric Acid, due to
the red color imparted by the dissolved Nitrogen Dioxide.

• Stream-11 is fed to the Bleaching Column, B101, where the secondary air strips
away the Nitrogen Dioxide, resulting in a clear, colorless 62% wt. Nitric Acid
Solution. The product acid (stream-14) is further cooled and stored in cylindrical
storage tanks.

5.3 Process Heat Integration

Nitric Acid Process is one of the world’s oldest and most researched industrial production
process. Hence, the intense amount of research that has gone into this process has led to
the latest iteration of the process flow to take shape, that we have incorporated into our
PFD. This process is highly integrated, from heat to energy. There was no requirement
to do a detailed heat integration study as the entire process has been well researched
and provided with the ample amount of heat and energy integration required to make
any nitric acid plant profitable in the smallest period of time.

The process has one main hot stream - Reactor outlet gas, coming out at a temperature of
890◦ C. It has to be cooled down to a temperature of 50◦ C before it enters the absorption
column. The first heat exchanger after the reactor is the Waste Heat Boiler, attached
directly to the reactor burner head. The gas flows through the shell side of this shell and
tube heat exchanger, with boiler feed water passing through the special boiler tubes,
made out of SA 192 and SA 213 - T12 Grade, to account for the evaporation and super
heating of the High Pressure steam produced in the boiler. This causes the temperature
of reaction mixture to drop to 427◦ C.

This HP Steam is used to run the Steam turbine used to run the common shaft, which
in turn drives the compressors. The LP Steam from the turbine is then used to super-
heat the evaporated ammonia entering the plant to a temperature of 70◦ C. Ammonia
Process Flow Diagram 26

evaporation utilises cooling water to evaporate the liquid ammonia. The water in turn
is cooled down to 7◦ C, where it can be used as chilled water, cooling the top section of
the absorption column.

After the Waste Heat Boiler, the NO gas is further cooled down to 295◦ C in the Tail
Gas Heater, by utilising the cold tail gas emanating from the absorption column. This
heats the tail gas to 350◦ C, temperature required by the abatement unit to function
properly. The NO gas is further cooled down to 185◦ C in the economiser. The cooling
stream here is the boiler feed water used in the Waste Heat Boiler, whose temperature
is increased from 40◦ C to 80◦ C.

The next two shell and tube heat exchangers are the largest heat exchanger in the plant.
The cooler condensers are utilised to cool down the reaction gases to 50◦ C, which helps
in forming the acid condensate. Cooling water is used in both the cooler condensers,
one before and one after the NOX compression.

The tail gas coming out of the Absorption Column is usually required to be reduced
in order to meet the government norms for NOX emissions. The abatement process
requires temperatures of around 350◦ C, and hence the tail gas, coming out at 10◦ C, is
first preheated in the Tail Gas Preheater to 130◦ C, with the help of the hot secondary air
used in the bleaching column, and further heated in the Tail Gas Heater as mentioned
in previous points. Once abated, the tail gas is used to drive a turbine, which provides
around 65% of the power required to drive the air and NOX compressors.

This integration is followed in all Dual Pressure Nitric Acid Processes, with slight vari-
ations in stream temperatures for processes from different technology providers. The
utility data is produced in a tabulated form below:

Utility Required Amount Required Utility Produced Amount Produced

Electricity 2465 kW
Cooling Water 0.437 MGal/hr
HP Steam (40 barg) 26680 kg/hr
Make Up Chilled Water 0.0134 MGal/hr
LP Steam 12600 kg/hr

Table 5.1: Utility Data after Heat Integration

The above mentioned Heat and Energy integration leads to the following heat exchanger
network:
 Process Flow Diagram

Figure 5.1: Heat Exchanger Network

27
 Process Flow Diagram

Figure 5.2: Process Flow Diagram for Dual Pressure Nitric Acid Process
28
Chapter 6

Mass Balance

This chapter provides a look at the mass balance performed on the process, with inputs
from Ray et. al1 . [8], source of the reference being DFPCL [7]. Some sample calculations
are also provided for some major equipment taking 100kmol/hr Ammonia as the basis.
All values were scaled up for the desired plant capacity.

6.1 Sample Calculations

6.1.1 Reactor - R101

Air is passed through a combination of primary and secondary filters and compressed
to 5 bar (240◦ C) from ambient conditions. Ammonia is evaporated from sub-zero tem-
peratures using water, passed through a preheater to raise the temperature to 70◦ C and
filtered to remove oils and particulate matter using the ammonia filters. Ammonia &
air are mixed in 1:9 ratio and the mixture enters the reactor at 230◦ C.

Reactor residence time is in few milliseconds where Pt-Rh catalyst provides the site for
reaction. Reaction occurs at 890◦ C which is maintained by the high exothermicity of
the reaction.
Main Reaction:

4N H3 (g) + 5O2 (g) → 4N O + 6H2 O, ∆H = −905kJ/mol

1
http://inspect.nigc.ir/Portal/Images/Images_Traning/files/files/chemist%20book/
Chemical%20Engineering%20Design%20Project%20-%20A%20Case%20Study%20Approach.PDF

29
Mass Balance 30

96% ammonia conversion is towards main reaction producing NO and the rest towards
side reactions:
Ammonia entering reactor = 100 kmol
NO formed: 100*(96/100) = 96 kmol
Required O2 for main reaction: 96*5/4 = 120 kmol
H2 O formed in main reaction: 96*3/2 = 144 kmol

Side Reaction 1:

4N H3 (g) + 3O2 (g) → 2N2 (g) + 6H2 O(g), ∆H = −1261kJ/mol

3% ammonia is consumed in side reaction 1:

Amount of N2 produced = 3/2 = 1.5 kmol
Amount of O2 required for side reaction = 1.5*3/2 = 2.25 kmol
Amount of H2 O produced in side reaction = 2.25*2 = 4.5 kmol

Side Reaction 2:

4N H3 (g) + 4O2 (g) → 2N2 O(g) + 6H2 O(g), ∆H = −1102kJ/mol

1% ammonia is consumed in side reaction 1:

Amount of N2 O produced = 1/2 = 0.5 kmol
Amount of O2 required for side reaction = 0.5*3/2 = 0.75 kmol
Amount of H2 O produced in side reaction = 0.75*2 = 1.5 kmol

Total water produced = 144 + 4.5 + 1.5 = 150 kmol

Total O2 consumed = 120 + 2.25 + 0.75 = 123 kmol

Similar calculations are made for all other equipment using their conversions and desired
outputs.

Components Reactor Feed (kmol/hr) Reactor Outlet (kmol/hr)

NH3 100 0
O2 189 66
N2 711 712.5
N2 O 0 0.5
H2 O 0 150
NO 0 96

Table 6.1: Reactor Balance

Mass Balance 31

6.1.2 Heat Exchangers and Cooler Condenser

The primary reaction that takes place next is the oxidation of nitric oxide to nitrogen
dioxide.
2N O(g) + O2 (g) → 2N O2 (g), ∆H = −114kJ/mol

This reaction takes place when the process gas is passed through a series of heat exchang-
ers and the conversion increases with reducing temperature. The process gas first passes
through Tail Gas Heater 1, where its heat is used to preheat the tail gas exiting from
the absorption column. It further passes through an economizer, used to preheat boiler
feed water and then through cooler condenser 1. By this point, the temperature of the
process gas comes down to 50◦ C, which is favourable for high nitric oxide conversion.
Simultaneously, water formed in the ammonia oxidation condenses, thereby dissolving
NO2 and forming HNO3 in small amounts as condensate.

3N O2 (g) + H2 O(l) → 2HN O3 (aq.) + N O(g), ∆H = −75kJ/mol

The conversion of NO in Tail gas heater 1 is ≈ 15%, in the economiser is ≈ 27% and
the concentration of acid condensate is ≈ 38%. These figures are similar to the DFPCL
data [7].

NOx
Reactor HE102 HE103 Acid
Comp.
Component Outlet Outlet Outlet Condensate
Inlet
(kmol/hr) (kmol/hr) (kmol/hr) (kmol/hr)
(kmol/hr)
O2 66 59 48 20 0
N2 712.5 712.5 712.5 712.5 0
H2 O 150 150 150 0 138
N2 O 0.5 0.5 0.5 0.5 0
NO2 0 14 36 56 0
NO 96 82 60 16 0
HNO3 0 0 0 0 24

Table 6.2: Heat Exchanger Balance

Mass Balance 32

6.1.3 Absorption Column and Cooler Condenser

The process gas (known as NOX gas) is compressed to 12 bar (165◦ C) and fed to cooler
condenser 2. The gas stream is then fed to the absorption column at the bottom and
acid condensate from cooler condenser 1 is fed at the middle of the column for further
concentration. Process water added at the top of the column at 20◦ C absorbs the NO2
forming HNO3 and NO formed as a side product gets oxidised back to NO2 by excess
air added to the column.

The acid leaving the column from the bottoms is 55%-60%wt which then passes through
the bleaching column to be stripped off of dissolved NOX gases. The tail gas leaving
from the tower of the tower is further sent for NOX abatement process to bring down
the NOX content to permissible levels. The basis for calculations on the column was the
empirical concentration of different NOX gases in the tail gas as 550ppmv.

Cooler
Acid Nitric Acid
Condenser 2 Tail Gas
Component Condensate Bottom
Outlet (kmol/hr)
(kmol/hr) (kmol/hr)
(kmol/hr)
NH3 0 0 0 0
O2 12.5 0 19.5 0
N2 713 0 808 0
H2 O 0 138 0 202.54
N2 O 0.5 0 0.5 0
NO2 71 0 0.06 7.82
NO 1 0 0.6 0
HNO3 0 24 0 94.42

Table 6.3: Absorption Column and Cooler Condenser Balance

6.2 Final Mass Balance Table

Above calculations were scaled to our desired production of 1500TPD of 62% Nitric Acid
Solution, providing us with the following results 2 :
2
All values are in kg/hr
 Mass Balance
Line No. Stream Comp. Phase NH3 O2 N2 H2 O N2 O NO2 NO HNO3 CO2 C3H8 Total Pressure (bar) Temperature (◦ C)
1 Air feed g 0 43519 145541 0 0 0 0 0 0 0 189060 1 35
1C Primary Air g 0 39005 128387 0 0 0 0 0 0 0 167391 5 240
1D Secondary Air g 0 4514 17154 0 0 0 0 0 0 0 21669 5 240
2 Ammonia Feed l 11003 0 0 0 0 0 0 0 0 0 11003 1 -33
2A Evaporated NH3 g 10963 0 0 0 0 0 0 0 0 0 10963 5 70
3 Reactor Inlet g 10963 39005 128387 0 0 0 0 0 0 0 178355 5 230
4 Reactor Outlet g 0 13570 128658 17412 142 0 18573 0 0 0 178355 5 427
5 HE102 Outlet g 0 12125 128658 17412 142 4153 15865 0 0 0 178355 5 300
6 HE103 Outlet g 0 9856 128658 17412 142 10680 11608 0 0 0 178355 5 185
7 Acid Condensate l 0 0 0 16019 0 0 0 9751 0 0 25770 12 50
8 NOx Comp. inlet g 0 8591 145812 0 142 18932 3096 0 0 0 176573 5 50
8A NOx Comp. Outlet g 0 8591 145812 0 142 18932 3096 0 0 0 176573 12 260
9 Absorption Inlet g 0 7043 145812 0 142 23382 193 0 0 0 176573 12 50
10 Tail Gas g 0 3307 145812 0 142 18 58 0 0 0 149336 12 130
11 Absorption Outlet l 0 0 0 23816 0 2320 0 38858 0 0 64993 12 50
12 Process Water l 0 0 0 11987 0 0 0 0 0 0 11987 12 10
13 Bleaching Air g 0 4514 17154 0 0 2320 0 0 0 0 23988 5 80
14 Nitric Acid Pdt l 0 0 0 23816 0 0 0 38858 0 0 62673 5 50
15 Mixed Tail Gas g 40 3307 145812 0 142 18 58 0 0 0 149376 12 350
16 Reduced Tail Gas g 0 3292 145966 87 2 1 2 0 42 0 149391 12 350
17 Tail Gas Out g 0 3292 145966 87 2 1 2 0 42 0 149391 1 35
18 Reducing Ammonia g 40 0 0 0 0 0 0 0 0 0 40 12 350
19 Propane g 0 0 0 0 0 0 0 0 0 15 15 12 350

Table 6.4: Final Mass Balance

33
Chapter 7

DWSIM Flowsheet Simulation

7.1 Kinetics and Specification used in DWSIM

The process explained in Chapter 5 is used to simulate a DWSIM flowsheet. Due to

unavailability of a few equipment in DWSIM, their modelling is done using different
alternatives. Centrifugal compressors and shell and tube heat exchangers are used where
ever required.

7.1.1 Ammonia Oxidation

Ammonia oxidation reaction in presence of Pt-Rh catalyst is highly selective and occurs
almost instantaneously, with residence time in the order of 10-4 - 10-3 seconds. Hence,
the available Conversion Reactor is used as an equivalent for the Shallow Bed Reactor
for optimised temperature and pressure conditions, giving a conversion of 96% for the
desired reaction. It is also assumed that almost all ammonia is consumed in the reactor,
either in the main reaction or in one of the side reactions.
The instantaneous nature of the reactions call for a millisecond reactor, which is why it
is difficult to use a kinetic model of this reaction in the simulation of the reactor. Only
one of the side reactions is considered in the DWSIM Flowsheet.

34
DWSIM Flowsheet Simulation 35

Figure 7.1: DWSIM Flowsheet - Ammonia Oxidation

7.1.2 Nitric Oxide Oxidation

In this step, the temperature of the stream is reduced which leads to the kinetic ox-
idation of NO to NO2 to move in the forward direction. Since the heat exchangers
cannot be modelled to include a reaction in them, plug flow reactors are used instead.
DWSIM PFRs give us the ability to calculate the heat duty for our required process,
while enabling us to model kinetic reactions, satisfying our requirements of reactive heat
exchangers.
2N O(g) + O2 (g) → 2N O2 (g), ∆H = −114kJ/mol

NO Oxidation is a third order reaction, with reaction rate and constant as,
2
Rate = 2kp CN O CO 2
530
logkp = + 7.09
T
Hence, the Arrhenius parameters required become, A = 1200 and E = -4406.42, values
taken from Tsukahara et. al. [9]

Water formed in the ammonia oxidation reaction reacts with absorbed NO2 to form
HNO3 . Since the reaction is mass transfer controlled, the kinetics involved in this
reaction are very difficult to model and therefore a simpler alternative used for this
reaction was to model an equilibrium reactor, with the equilibrium reaction,

3N O2 (g) + H2 O(l) 2HN O3 + N O(g), ∆H = −75kJ/mol

DWSIM Flowsheet Simulation 36

with Kp being the equilibrium constant, given by Thiemann et. al. [6] as,
logKp = −7.35 + 2.64/T

Cooler Condenser is modelled using a PFR to take into account the NO Oxidation,
followed by an Equilibrium Reactor to model the Nitric Acid formation and a Gas-
Liquid Separator to produce Acid Condensate and NOX gas.

Figure 7.2: DWSIM Flowsheet - NO Oxidation and Heat Exchanger Network

7.1.3 Absorption Column

The separated streams are sent to the absorption column. In the absorption column,
the NO2 is absorbed in water and reacts to form HNO3 and NO, which is again oxidised
to form NO2 , and so on. Modelling of a reactive absorption column was done using a
ChemSep column, with the specified reactions used in the unit. Issues propped up as
the desired conversion couldnt be achieved, hence a different approach was used. The
column was divided into two parts- Absorption and Reaction. A Simple Absorber was
used to facilitate NOX absorption into water, followed by a series of reactors to model
the NO Oxidation and Nitric Acid formation reactions. Two recycle streams were used
in this part, to recycle back the unconverted gases, to achieve the given conversions and
concentrations.
DWSIM Flowsheet Simulation 37

Figure 7.3: DWSIM Flowsheet - Reactive Absorption Column Modelling

7.2 Comparisons

7.2.1 Ammonia Reactor

Reactor Inlet Reactor Outlet

Manual DWSIM Manual DWSIM
NH3 10963 11000 0 0
NO 0 0 18573 18605
NO2 0 0 0 0
HNO3 0 0 0 0
H2 O 0 0 17412 17452
N2 128387 128397 128658 128775
O2 39005 38993 13570 13568
Total 178353 178400 178353 178400

Table 7.1: Mass Balance Comparison for Reactor

DWSIM Flowsheet Simulation 38

7.2.2 Heat Exchangers

Reactor Outlet Cooler Condenser Inlet

Manual DWSIM Manual DWSIM
NH3 0 0 0 0
NO 18573 18605 11608 12024
NO2 0 0 10680 10044
HNO3 0 0 0 0
H2 O 17412 17452 17412 17452
N2 128658 128775 128658 128775
O2 13570 13568 9856 10069
Total 178355 178400 178353 178400

Table 7.2: Mass Balance Comparison for Heat Exchanger network

7.2.3 Absorption Column

Gas Inlet Combined Outlet

Manual DWSIM Manual DWSIM
NH3 0 0 0 0
NOx 22288 22068 76 100
HNO3 0 0 38858 38800
H2O 17412 17452 23816 24000
O2 9856 10069 3307 3500
Total Inlet/Outlet Flow rate 178355 178400 178355 178400

Table 7.3: Mass Balance Comparison for Absorption Column

Chapter 8

Sensitivity Analysis

8.1 Reactor Analysis

Figure 8.1: Sensitivity Analysis for Reactor

The optimum temperature at which the reaction should be done is between 860 - 920◦ C.
We are operating our reactor at 890◦ C.

39
Sensitivity Analysis 40

8.2 Heat Exchanger simulated as PFR

Figure 8.2: Sensitivity Analysis for Heat Exchanger

On increasing the volume, the mole fraction of nitrogen dioxide increases to a certain
value, and becomes constant after around 0.9 m3 .
Sensitivity Analysis 41

8.3 Absorption Column Analysis

Figure 8.3: Sensitivity Analysis for Absorption Column - 1

Figure 8.4: Sensitivity Analysis for Absorption Column - 2

The above analysis compares the Nitric Acid Solution Flow rate and Concentration as
a function of extra added air. The minimum amount of extra O2 required is 1kg/s
which provides us with the best results, the selected O2 rate was set at 1.25 kg/s, which
Sensitivity Analysis 42

provided us with the least amount of NOX in the tail gas as well. The mentioned
comparisons are for the said extra O2 values, which are obtained from the secondary
air, and can be manipulated using the split ratio and intake of air.
Chapter 9

Equipment Sizing and Costing

In this chapter, we size the major equipments used in the plant and also estimate the
cost of each of the equipment. They are listed in the following sections. The following
data is used in the cost estimation:

• India location index w.r.t US = 0.7

• Dollar to INR = 70

• Cost Index - Chemical Engineering Plant Cost Index

• All equipment cost are f-o-b basis

• Direct and Indirect Costs in FCI are calculated using percentage normalisation
from Peters et. al. [10]

• Equipment Cost is estimated using Nomograms from Peters et. al. [10] and Walas
et. al. [11]

• All equipment are mapped to the average 2018 Cost Index - 603.1 (As of Dec 18),
data acquired from ChemEngOnline Website 1 [12]

9.1 Ammonia Oxidation Reactor

The Ammonia Oxidation Reactor is a shallow bed reactor, with a burner head and 90-10
Pt-Rh gauzes as its main parts. Since Pt-Rh Gauzes have a lifetime of 6-8 months, only
1
https://www.chemengonline.com/pci

43
Equipment Sizing and Costing 44

first 24 months of the catalyst gauzes will be capitalised and the rest will be incorporated
into the Operating Costs. The burner head is a pressure vessel head, with a conical shape
and operating pressure of 5 bar abs. Since the burner head doesnt come under the direct
heat of the reaction gases (890◦ C), we dont require any special material of construction
for the said equipment.

9.1.1 Diameter Calculation

The diameter of the gauzes and that of the burner head are calculated using the following
data provided by Krupp Uhde2 [13]

1. Gauze Density - 400g Pt/m2 of gauze

2. Amount of Nitrogen allowed on Gauze to provide desired conversion - 10 Tonnes

per day of N/m2 of gauze

3. Platinum required for given Nitrogen - 320g Pt/Tonne per day Nitrogen

NH3 consumed = 3.056 kg NH3/s = 0.17974 kmol NH3/s = 179.74 mol N/s
= 2.516 kg N/s = 219.608 tonnes N/day
From 2., we get, Area required, A = 21.961 m2
Hence, Diameter = 5.288 m
From 3., we get, Pt required = 70.275 kg
From 1., we get, Pt/gauze = 8.784 kg
Hence, we get, Number of Gauzes = 70.275/8.784 = 8 gauzes

9.1.2 Catalyst Costs

Platinum and Rhodium prices were acquired from [14]3 and [15]4 respectively. Since the
catalyst life is 6 months, we are using 2 batches of catalyst gauzes per year. We are also
capitalising 24 months worth of catalyst.
2
Mr. Amrish Dholakia, Thyssenkrupp Industrial Solutions
3
https://www.goldpriceindia.com/
4
http://www.infomine.com/investment/metal-prices/rhodium/
Equipment Sizing and Costing 45

Catalyst Required / year Catalyst Cost / kg Catalyst Cost / year

(kg) (USD) (INR)
140.55 34,750 48.837 Lakhs

Table 9.1: Catalyst Costs

Capitalised Catalyst Cost = 140.55 * 2 * 34750 * 70

= INR 97,67,475.1 = INR 97.675 Lakhs

9.1.3 Burner Head Calculation

The burner head is vertical, conical vessel with the following specifications:
Corrosion Milling Design Design
Sa Weld Joint
α(◦ ) Di (m) MoC Allowance Tolerance Temp. Pressure
(MPa) Efficiency (E)
(c) (m) (C) (barg)(P)
45 5.3 SS 321 0.5 mm 12.5 190 500 4.4 1

Table 9.2: Burner Head Design Parameters

According to the Internal Pressure Vessel calculations, to find the regulation thickness,
t, referring to CL 407 Handouts [16],
P Di
t=
2 cos α[Sa E − 0.6P ]
Hence we get, t = 11.7 mm. Now to get the trec , we have,
t+c
trec = m = 14mm
1 − 100
Hence, weight of the Burner head = 6,336.2 lbs
From Walas et. al. [11], we have Vertical Pressure Vessels cost, C as (The Formula
provides values for 1984 in US$ with CE Cost Index = 315),
C = FM Cb + Ca
Cb = 1.672exp[9.1 + 0.2889(lnW ) + 0.04576(lnW )2 ]

Ca = 480D0.7396 L0.7066

where W - shell weight in lbs, D - Diameter in ft and L - Height in ft. On using the
required values we get the following results:

D L FM Cost Cost Cost (INR)

W (lbs) Cb Ca
(ft) (ft) (SS 321) ($, in 1984) ($, in 2018) (Including fob)
6,336.20 6.6 8.7 23805.9 4562.2 1.87 49,079.10 105,883.20 72.36 Lakhs

Table 9.3: Burner Head Costing Parameters

Equipment Sizing and Costing 46

Hence, cost to construct the burner head = INR 72.36 Lakhs

9.2 Storage Tanks

We produce 62% Nitric Acid solution at 1500 tonnes/day, which corresponds to 45.2
m3/h. Referring to Walas et. al. [11] we will require a Field Erected Storage Tank
of height 20 m and diameter 33 m with a capacity of 4.5 million gallons, keeping an
inventory of 15 days of Nitric Acid. Nitric Acid Solution is stored under ambient atmo-
spheric conditions. We also require an Ammonia Storage Tank to store our Ammonia
for a period of one month to account for imports and procurement of the raw material.
Ammonia is stored at -33◦ C and 1 atm abs. For this, special Double walled Tanks are
constructed on site with a refrigeration unit accompanying the same. Ammonia required
is 267 tonnes/day, which corresponds to 16.5 m3/h. Referring to Fertilizers Manual [17],
we will require a LT Carbon Steel Refrigerated Double Walled Storage Tank, of height 20
m and diameter 28 m with a capacity of 3.25 million gallons. Suggestions for inventory
were given by Krupp Uhde [13].

Referring Fertilizers Manual [17], Refrigerated Double Walled Ammonia Storage Tank
incurred a capital cost of $ 3.22 million in 1992-1994. Using CE Cost Index of 360 for
the said period, multiplying CE Cost Index of 2018, 603.1, and multiplying $ to INR
conversion factor of 70 and 1.1 to include f-o-b, we get,
Refrigerated Ammonia Storage Cost = INR 41.52 Crores
The following relation is used for costing of Field Erected Storage Tanks (C calculated
in $, all values for 1984 with CE Cost Index = 315):

C = FM exp[11.662 − 0.6104(lnV ) + 0.04536(lnV )2 ]

where V - Volume in Gallons and FM - MoC Factor

Temp.
Storage Dim. Volume C C Cost (INR)
And MoC FM
Tank (m) (gal) ($, 1984) ($, 2018) (Including fob)
Pressure
Nitric Acid D = 33 T = 30◦ C 4.52
SS 304 2.4 1,019,978.60 1,952,854.30 15.04 Crores
Storage H = 20 P = 1 atm million

Table 9.4: Nitric Acid Storage Tank Costing

Hence, the total cost required for Storage Tanks = INR 56.56 Crores
Equipment Sizing and Costing 47

9.3 Compressors

There are two compressors in the plant - C101 to compress the Air feed from ambient
conditions to 5 bar abs before the Ammonia Oxidation Reactor and C102 to compress
the oxidised NOX gases to a pressure of 12 bar, for the high pressure absorption column.

Both the compressors are Two Stage Centrifugal Compressors with turbines, with the
Air Compressor, C101 having a compression ratio of 2.236 and the NOX Compressor,
C102 having a compression ratio of 1.549. The choice to use a multi-stage compressor
was made because the temperature increase due to compression in one single stage
could have damaged the compressor in both the cases and also due to the fact that the
power requirements and the flow rates were in the range of the operating conditions for
centrifugal compressors.

Calculations are shown for the first stage of the C101, Air Compressor, with Air coming
at 189.06 tonnes/hour.

Power = Work rate / Isentropic Efficiency = W / η

n P2 n−1
W = P1 V 1 [( ) n − 1]
n − 1 P1

P1 - Inlet Pressure = 1 bar

P2 - Outlet Pressure = 2.266 bar
V1 - Volumetric Flow = 49.21 m3 /s
n - Heat Capacity Ratio = 1.4
Isentropic Efficiency, η = 0.85 (Ref - Krupp Uhde [13])

On solving the given equation, we get, Power = 5307.05 kW

Similar calculations for other stages and compressors yield the following results:

Inlet Pressure Outlet Pressure Power Required

Compressor Stage
(bar) (bar) (kW)
C101 1 1 2.236 5237.5
C101 2 2.236 5 7042.9
C102 1 5 7.745 2037.2
C102 2 7.745 12 2350.1

Table 9.5: Compressor Power Calculation

Equipment Sizing and Costing 48

For cost estimation, Nomograms from Peters et. al. [10] are used. Referring the nomo-
grams, we get the following results for the compressor cost estimation:

** Note that both the compressors are Two Stage Centrifugal Compressors
with Turbines

Equip. Power
Pin - Pout Process Cost Cost Cost INR
No. - Required MoC
(bar) Fluid ($, 2002) ($, 2018) (Including fob)
Stage (kW)
P1 = 1 36.88
C101 - 1 Air 5237.5 CS 3.1 million 4.789 million
P2 = 2.236 Crores
P1 = 2.236 49.96
C101 - 2 Air 7042.9 CS 4.2 million 6.488 million
P2 = 5 Crores
P1 = 5 16.65
C102 - 1 NOX Gas 2037.2 SS 304L 1.4 million 2.163 million
P2 = 7.745 Crores
P1 = 7.745 19.04
C102 - 2 NOX Gas 2350.1 SS 304L 1.6 million 2.472 million
P2 = 12 Crores

Table 9.6: Costing of Multi Stage Compressors with Turbines

Hence, total cost required for Compressors = INR 122.53 Crores

9.4 Pumps

There are a total of 6 estimated pumps in the plant. Including standby pumps, we have
a total of 12 pumps. Out of these 12, 6 are part of the cooling circuit of absorption
column and their cost is incorporated into the costing of the absorption column using
the data provided by Krupp Uhde [13]. Out of the remaining pumps, one set is used to
pump liquid ammonia into the plant, one set is used to pump the acid condensate to the
absorption column and the last set is used to pump the required water into the boiler for
production of steam. Sample calculation for the liquid Ammonia pump is shown below.

Liquid Ammonia is fed at 19 bar to the Ammonia evaporator from the Ammonia Storage,
which stores ammonia at 1 bar and -33◦ C. Since the temperature is so low, LT Carbon
Steel is used as the MoC of this pump.

Flow rate = 3.056 kg/s; Pressure difference = 18 bar; Density of liquid = 610 kg/m3

We know that, Pump Work,

∆P ∆Pf
WP = + g∆z +
ρ ρ
Equipment Sizing and Costing 49

Hence we get, Pump Work, WP = 2.992 kJ/kg

Power required = WP * Flow Rate/pump efficiency(assumed to be 0.85) = 10.757 kW

All pumps used here fall under the zone of Centrifugal Pump considering the flowrate
and the head required. The following relations from Walas et. al. [11] are used to
estimate individual pump costs, C (Calculated values in $ for 1984, with CE Cost Index
= 315):
C = FM FT Cb , base cast − iron, 3550 rpm, V SC
√ √
Cb = 3exp[8.833 + 0.6019(lnQ H) + 0.0519(lnQ H)2 ]
√ √
FT = exp[b1 + b2 (lnQ H) + b3 (lnQ H)2 ]

Type b1 b2 b3
One-stage, 1750 rpm, VSC 5.1029 -1.2217 0.0771
One-stage, 3550 rpm, HSC 0.0632 0.2744 -0.0253
One-stage, 1750 rpm, HSC 2.029 -0.2371 0.0102
Two-stage, 3550 rpm, HSC 13.7321 -2.8304 0.1542
Multistage, 3550 rpm, HSC 9.8849 -1.6164 0.0834

Table 9.7: Pump Costing Factors

Flow Range Head Range HP

Type
(gpm) (ft) (max)
One-stage, 3550 rpm, VSC 50-900 50-400 75
One-stage, 1750 rpm, VSC 50-3500 50-200 200
One-stage, 3550 rpm, HSC 100-1500 100-450 150
One-stage, 1750 rpm, HSC 250-5000 50-500 250
Two-stage, 3550 rpm, HSC 50-1100 300-1100 250
Multi-stage, 3550 rpm, HSC 100-1500 650-3200 1450

Table 9.8: Pump Factors

Based on the tables and cost relations provided above, we get the following results for
the pump cost estimations:

** Note - All the above mentioned Pumps are Centrifugal pumps. Cost
include the costing of both A/B pumps for each set
Equipment Sizing and Costing 50

Flow
Process Head Type - Cost Cost Cost INR
Pump rate
Fluid (ft) MoC ($, 1984) ($, 2018) (Including Fob)
(gpm)
Two-Stage,
P101 Liquid
79.5 1001.2 3550 rpm, 17,233.40 32,995.10 25.41 Lakhs
(A/B) Ammonia
HSC - CS
One-Stage,
P102 Nitric
127.7 250.1 3550 rpm, 17,495.30 33,496.50 25.80 Lakhs
(A/B) Acid
HSC - SS 304
Boiler One-Stage,
P103
Feed 52.6 322.5 3550 rpm, 7,721.50 14,783.60 11.39 Lakhs
(A/B)
Water VSC - CS

Table 9.9: Costing of Centrifugal Pumps

Hence, the total cost required for Pumps = INR 62.60 Lakhs

9.5 Heat Exchangers

There are a total of 8 Heat Exchangers in the plant. All the heat exchangers are Shell
and Tube Heat Exchangers, as verified from Krupp Uhde [13] and DFPCL [7]. The
waste heat boiler is sized below.

Cooling Agent - Water at 80◦ C, 6 bar

NOX Gas from Reactor is cooled from 890◦ C to 427◦ C

Water boils and is converted to steam, which is superheated to 380◦ C

TLMTD = 405.4◦ C

Overall Heat Transfer Coefficient for Gas-Water Heat Exchange, U = 150 W/(m2.K)

Q = 26063.9 kW and we know that, Q = U A ∆TLMTD . Hence, we get,

A = Q / (U * TLMTD ) = 428.62 m2

The cost estimate for heat exchangers is performed using the nomograms available in
Peters et. al. [10], where the cost from nomogram was in $ for 2002, with CE Cost
Index = 390.4:
Equipment Sizing and Costing 51

HE101- HE101-
HX No. WHB HE102 HE103 HE104 HE105 HE106
AE AS
Cooling
Hot Stream LP Steam NO Gas NO Gas NO Gas NO Gas NO Gas Air
Water
Thot, in (K) 306 423 1123 700 568 457 530 493
Thot, out (K) 280 372 700 568 457 323 323 323
Cold BFW/ Cooling Cooling
Ammonia Ammonia Tail Gas BFW Tail Gas
Stream Steam Water Water
Tcold, in (K) 240 283 353 403 313 306 306 283
Tcold, out (K) 283 343 653 623 353 330 330 403
Q (kW) 4472 412.7 26063.9 8667.8 7282.3 13883.7 5765.7 4675.1
U (W/m2 .K) 150 300 150 95 150 150 150 95
Area (m2 ) 970.5 16.3 428.7 790.2 274.1 1692.1 517.8 798.2
Shell Side
Ammonia LP Steam NO Gas Tail Gas BFW NO Gas NO Gas Air
Fluid
Shell Side SS 304L SS 304L
LT CS CS SS 321 SS 321 SS 304L SS 304L
MoC 2Re10 2Re10
Tube Side Cooling BFW/ Cooling Cooling
Ammonia NO Gas NO Gas Tail Gas
Fluid Water Steam Water Water
Tube Side SA 192/ SS 304L SS 304L
LT CS SS 321 SS 304L SS 304L SS 304L
MoC SA 213 2Re10 2Re10
Pressure Tube:12
6.5 5 5 5 5 5 12
(bar abs) Shell:5
Cost
54,150 5,054 197,534 191,301 60,078 704,968 346,418 177,650
($ , 2002)
Cost
83.7 7.8 305.2 295.5 92.8 1,089.10 535.2 274.4
(1000$, 2018)
Cost INR 0.65 0.061 2.35 2.28 0.72 8.39 4.12 2.11
(Including fob) Crores Crores Crores Crores Crores Crores Crores Crores

Table 9.10: Operating Parameters and Costing of Heat Exchangers

** Note - SS 304L 2Re10 is a special material provided Sandvik Materials

Technology. The cost factor of this material is used as 3X of SS 304L accord-
ing to the data provided by Krupp Uhde. Also SA 192 and SA 213 are high
temperature corrosion resistant Alloys, for which cost factor used is 2X SS
304L according to the data provided by Krupp Uhde [13].

Hence, the total cost required for Heat Exchangers = INR 20.67 Crores
Equipment Sizing and Costing 52

9.6 Columns

We have two Absorption Columns in our plant, one is a 47 m tall reactive absorption
column and the second one is a 10 m tall bleaching column. Since the absorption column
has a height greater than 10 m, we need to make thickness calculation based on stresses
produced due to wind at heights. We can ignore this for the shorter bleaching column.
We use internal pressure vessel and wind force calculations to find out the thickness
required for the column body and heads.

9.6.1 Shell Calculations

Using Internal Pressure Vessel calculations, referring to CL 407 Handouts [16], we have,
P Di
t=
2[Sa E − 0.6P ]

P = 12.1 bar, Di = 4m, Sa for MoC SS 304L = 180MPa, E = 0.9.Hence we get, t = 15

mm. Now to get the trec , we have,
t+c
trec = m = 14mm
1 − 100

Using c = 1mm and m = 12.5, we get trec = 18.3 mm

Both the columns have ellipsoidal heads, using details from CL 407 Handouts [16],
similar calculations are done for the heads and the skirt. The details of the calculations
are provided in the detailed design of the absorption column. Following the thickness
calculations, weights of the columns were calculated, skirts and heads included.

** Note - The bottom closure of the absorption column, A101 has a separate
vessel attached inside, with its weight being 0.25 times that of the closure
itself, according to the data provided by Krupp Uhde [13].

** Note - The Absorption Column comes with a cooling system, inclusive of a

piping network and 4 pumps. According to the data provided by Krupp Uhde
[13], once the entire column cost is calculated, including trays, multiplying a
factor of 1.25 will give a rough estimate for the entire column cost including
the cost of the cooling system.

Nomograms from Peters et. al. [10] are used, where the cost from nomogram was in $
for 2002, with CE Cost Index = 390.4:
Equipment Sizing and Costing 53

A101 - B102 -
Column
Absorption Column Bleaching Column
Height (m) 44.6 9
Diameter (m) 4 1.75
Tray Spacing 1 m / 1.2 m 0.6 m
trec for Body (mm) 18.3 4.55
trec for Heads (mm) 18.24 4.54
trec for Skirt (mm) 3.77 3.77
Skirt Height (m) 3.4 1
NO-NOx Gases, Air, NOx Gases,
Fluids Processed
Nitric Acid Nitric Acid
Operating Pressure
11 4
(barg)
Operating Temp.
10 - 50 30 - 50
Range (C)
MoC SS 304L SS 304L
Weight (Tonnes) 88.46 2.006
Cost ($, 2002) 700,000 52,000
Cost ($, 2018) 1,081,378 80,331
Cost INR(Including fob) 8.33 Crores 0.62 Crores

Table 9.11: Column Parameters and Costing

9.6.2 Tray Calculations

Sieve trays are used in both the absorption columns due to there many benefits. Selection
process, the tray specification and calculations for number of trays for absorption column
are all specified in the detailed design of the absorption column.

Nomograms from Peters et. al. [10] are used for cost estimation, where the cost from
nomogram was in $ for 2002, with CE Cost Index = 390.4:
Equipment Sizing and Costing 54

Per Tray Total Tray

Diameter Number of Cost INR
Column MoC QF Cost Cost
(m) trays (Including fob)
($, 2002) ($, 2018)
1.68
A101 4 36 SS 304L 0.98 4,000.00 239,807.00
Crores
0.30
B102 1.75 12 SS 304L 1.4 1,400.00 42,823.00
Crores

Table 9.12: Sieve Tray Costing

Shell Costs Tray Costs Total Purchased Cost

Column
(INR, 2018, fob) (INR, 2018, fob) (INR, 2018, fob)
A101 8.33 Crores 1.68 Crores 12.51 Crores
B102 0.62 Crores 0.30 Crores 0.92 Crores

Table 9.13: Total Purchased Costs for Columns

Hence, the total cost required for Columns, including the cooling system = INR 13.43
Crores
Chapter 10

Plant Economics

This chapter focuses on an overview of the plant economics, by estimating the capital
investments, production costs and finally the payback period for the Nitric Acid Plant.

10.1 Major Equipment Costing

The Dual Pressure Nitric Acid plant has many major equipments including storage
tanks, compressors, pumps, heat exchangers, reactor and columns. We used costing
relations provided by Peters et. al. [10] and Walas et. al. [11] to determine the
purchased cost including f-o-b of each of these equipments, using CE Cost index to find
their costs in 2018. A dollar to INR factor of 70 is used and an India location factor of
0.7 is also used. The following is the final result of our calculations in Chapter 9:

Table 10.1: Total Purchased Equipment Cost

Equipment Total Purchased Cost, INR (2018, fob)

Reactor 1.700 Crores
Storage Tanks 56.56 Crores
Compressors 122.53 Crores
Pumps 62.60 Lakhs
Heat Exchangers 20.67 Crores
Columns 13.43 Crores
Total Purchased Equipment Cost 215.51 Crores

55
Plant Economics 56

10.2 Capital Investment Estimation

Total purchased equipment costs calculated in the prvious section are used to calculate
the total capital investment in the plant. Working capital is calculated as 15% of the
total capital investment. The plant is considered to be a Fluid-Fluid Processing plant
(F-FPP) and the percentage of delivered equipment cost is implemented for this cost
estimation. The results of the estimation are provided in the table below:

Direct Costs F-FPP Normalized % Cost (Cr. INR)

Purchase Equipment Delivered 100 0.1984 215.51
Purchsed Equipment Installation 47 0.0933 101.29
Instrumentation and controls 36 0.0714 77.58
Piping 68 0.1349 146.54
Electrical Systems 11 0.0218 23.71
Buildings 18 0.0357 38.79
Yard Improvements 10 0.0198 21.55
Service Facilities 65 0.1290 140.08
Land 5 0.0099 10.78
Total direct plant cost 360 0.7143 775.82

Indirect Costs
Engineering and Supervision 33 0.0655 71.12
Construction Expenses 41 0.0813 88.36
Legal Expenses 4 0.0079 8.62
Contractor’s Fee 22 0.0437 47.41
Contingency 44 0.0873 94.82
Total indirect plant cost 144 0.2857 310.33

Fixed Capital Investment 504 1.0000 1086.15

Working Capital
191.67
(15% of total capital investment)

Total Capital Investment 1277.82

Table 10.2: Total Capital Investment Estimation

Plant Economics 57

Peters et. al. [10] is used as the reference for this costing exercise, using the ratio factors
provided by it for our cost estimation.

Using an India Factor of 0.7, we get,

Total Capital Investment = INR 894.48 Crores

10.3 Raw Material Cost

The estimation of the total product cost comes from raw material cost. We require
Liquid Ammonia as a raw material, which is acquired via imports and from KRIBHCO,
and we also require 140.55 kg of Pt-Rh catalyst gauzes every year, acquired from Johnson
Matthey India Pvt. Ltd. Raw material cost calculation is provided below:

Raw Material Amount Cost/kg ($/kg) Cost/year ($/year)

Ammonia 267 tonnes/day 0.429 37.35 Million
Pt-Rh Gauze 140.55 kg/year 34,750 4.884 Million
Total Raw Material Cost 42.24 Million

Table 10.3: Total Raw Material Cost Calculation

Hence, the Total Raw Material Cost = $ 42.24 Million / year

10.4 Revenue Calculation

The plant revenue is calculated from the untaxed prices of 62% Weak Nitric Acid (WNA)
Solution, sold at INR 20/kg1 . The results are tabulated below:

Product Amount Cost/kg ($/kg) Cost/year ($/year)

62% WNA Solution 1520 tonnes/day 0.286 141.82 Million

Table 10.4: Total Revenue Calculation

Hence the Total Revenue = $ 141.82 Million / year

1
https://www.zauba.com
Plant Economics 58

10.5 Total Product Cost

Total Product cost is calculated using the normalised percentage method from Peters
et. al. [10].The result is reproduced in the following tabulated form:

Category Factor Norm Cost ($/yr)

Raw material 45 0.3460 42.23 Million
Operating Labour 10 0.0769 9.385 Million
Supervising Labour 3 0.0231 2.815 Million
Utilities 15 0.1153 14.08 Million
Repairs and Maintenance 7 0.0538 6.569 Million
Operating supplies 1.05 0.0081 0.986 Million
Laboratory charges 1.5 0.0115 1.408 Million
Patents 3 0.0231 2.815 Million
Fixed charges 15 0.1153 14.08 Million
Plant overhead 12 0.0923 11.26 Million
Admin costs 1.5 0.0115 1.408 Million
Distribution and marketing 11 0.0846 10.32 Million
RnD cost 5 0.0384 4.692 Million
Total 130 1.0000 122.048 Million

Table 10.5: Total Product Cost Estimation

Hence, the Total Product Cost = $ 122.048 Million / year

10.6 Payback Period

The following assumptions were made while making the payback period calculations:

• 90% of FCI excluding the land costs is considered to be depreciable over a period
of 10 years.

• Average depreciation is calculated using linear depreciation model.

• Bank interest rate of 6% over the total capital is also used, referring data provided
by Krupp Uhde [13].
Plant Economics 59

• Final Product and Raw Material costs are assumed to be constant for profit cal-
culations.

Total Depreciable FCI = INR 677.49 Crores

Total Depreciation per year = INR 67.749 Crores / year

Taxation Rate, including surcharge and education cess = 28.3% = 0.283

Total Product Cost = $ 122.048 Million = INR 854.33 Crores / year

Revenue = $ 141.82 Million = INR 992.74 Crores / year

Bank Interest Rate = 6%

Gross Profit = Revenue - Total Product Cost - Depreciation per year

= INR 70.658 Crores

Net Profit = Gross Profit * (1 - Taxation Rate) = INR 50.662 Crores

Interest on TCI = Bank Interest Rate * TCI = INR 53.669 Crores

Depreciable F CI + interest on T CI
P ayback P eriod =
Avg. P rof it/yr + Avg. Depreciation/yr

Using 70% production capacity for year 1, 80% for year 2, 90% for year 3 and 100%
thereafter, the following cash flow diagram was generated,

Gross Net Cash Cumulative Capacity

Year Investment Cost Revenue Depreciation
Profit Profit Flow Position (%)
0 -760.31 -760.31 -760.31
1 -598.03 694.92 96.88 56.46 26.68 83.14 -677.17 70
2 -683.47 794.19 110.72 56.46 35.82 92.27 -584.89 80
3 -768.90 893.47 124.57 56.46 44.95 101.41 -483.48 90
4 -854.33 992.74 138.41 56.46 54.09 110.54 -372.94 100
5 -854.33 992.74 138.41 56.46 54.09 110.54 -262.40 100
6 -854.33 992.74 138.41 56.46 54.09 110.54 -151.85 100
7 -854.33 992.74 138.41 56.46 54.09 110.54 -41.31 100
8 -854.33 992.74 138.41 56.46 54.09 110.54 69.23 100
9 -854.33 992.74 138.41 56.46 54.09 110.54 179.78 100
10 -854.33 992.74 138.41 56.46 54.09 110.54 290.32 100

Table 10.6: Cash Flow from Plant production, all values in INR Crores
Plant Economics 60

Figure 10.1: Estimated Cash flow from Plant Operation

Hence, Payback Period = 7.3 Years

All the data has been cross checked with the data provided by Krupp Uhde [13]. The
following comparison with economics of a 500TPD Dual Pressure Plant set up in Don-
aldsonville, Louisiana, United States by Uhde in collaboration with CF Industries in
2016, shows that our plant economics are in accordance with actual industry economics.

Our Plant Uhde Plant

Location Hazira, Gujarat, India Donaldsonville, Louisiana, US
Capacity (TPD)
942 500
(100% NA)
Total FCI (INR) 761 Crores 450 Crores
Payback Period (yrs) 7.3 7

Table 10.7: Plant Economics Comparison with recently setup plant

Chapter 11

Detailed Design - Absorption

Column

The dual pressure process, requires an absorption column to absorb NOX gases from
the gaseous reactor into water and produce the desired concentration of nitric acid. The
column handles three streams - (1) gas stream at 1,76,573 kg/hr, containing 13.35% by
weight of nitrogen oxides at 50◦ C and 12 bar, (2) deionised make up water at 11,987
kg/hr, 10◦ C and 12 bar and (3) 37.8% nitric acid condensate from cooler condensers, at
25770 kg/hr, 50◦ C and 12 bar. The column is required to produce 62,673 kg/hr of 62%
HNO3 solution, excluding the dissolved NOX gases.

A sieve tray absorption column is proposed, with a column diameter of 4 m, height of

44.6 m, 36 cross-flow type trays with spacings of 1m and 1.2 m between trays. The
operating pressure is approximately 12 bar abs, with an operating temperature range of
10C - 50C.

A rigorous mathematical model was also produced for this column, to determine the
exact number of trays for the entire column, using correlations and data from Ray et.
al. [8] and Thiemann et. al. [6]. The model was run using MATLAB and Google
Spreadsheets.

61
Detailed Design - Absorption Column 62

11.1 Mathematical Model

A rigorous mathematical model was used in sizing the column and determining the exact
number of trays required for our column. The model is summarised below:

• Tray by tray approach based on the given feed compositions, temperatures and
pressure is implemented

• First, NO oxidation conversion is calculated using correlations from Ray et. al. [8]
and gas composition is recalculated - Step 1

• Next, NO2 dimerisation equilibrium with N2 O4 is calculated by solving a quadratic

equation provided by Ray et. al. [8], giving us the required partial pressure of
NO2 , and the gas composition is calculated again - Step 2

• Next, the amount of nitric acid formed in each plate is calculated using tray effi-
ciency and related terms, available in Ray et. al. [8] and derived from Thiemann
et. al. [6], and both liquid and gas phase compositions are recalculated - Step 3

• NO2 - N2 O4 equilibrium is recalculated, leading to another recalculation of the gas

composition - Step 4

• Method is repeated until a tray achieves an almost zero concentration nitric acid.
Tail Gas composition and the required amount of make up water are calculated at
the end.

The model was solved using an iterative method, implemented by solving 3 functions
iteratively on MATLAB R2015b, using the fsolve function. Solutions from MATLAB
were iteratively fed to Google Spreadsheets for the gas composition recalculation, as
MATLAB R2015b didnt allow for the functions to defined within its for loops. The
code can be found in the Appendix A.

Reactions occurring in the Absorption column -

2N O + O2 → 2N O2 , ∆H = −112.7kJ/mol

2N O2 N2 O4 , ∆H = −58.1kJ/mol
3
N2 O4 + H2 O 2HN O3 + N O, ∆H = −75.0kJ/mol
2
The results of the mathematical model are tabulated below:
Detailed Design - Absorption Column 63

Tray Tray Nitric Acid Energy Cooling

X Fa
Number Spacing(m) Conc.(wt%) (kJ/s) Water(kg/s)
1 1.5 0.6200 0.8786 0.0145 -2369.3334 28.3413
2 1 0.5939 0.8077 0.0126 -2184.3813 26.1290
3 1 0.5691 0.7909 0.0114 -2062.5688 24.6719
4 1 0.5448 0.7730 0.0103 -1901.1506 22.7410
5 1 0.5210 0.7547 0.0092 -1713.0681 20.4912
6 1 0.4982 0.7363 0.0082 -1537.1034 18.3864
7 1 0.4764 0.7183 0.0072 -1373.5775 16.4304
8 1 0.4561 0.7099 0.0065 -1236.6114 14.7920
9 1 0.4368 0.6839 0.0058 -1101.8346 13.1798
10 1 0.4186 0.6678 0.0052 -997.0431 11.9264
11 1 0.4015 0.6524 0.0046 -890.6925 10.6542
12 1 0.3857 0.6379 0.0041 -799.0663 9.5582
13 1.2 0.3710 0.6727 0.0038 -1546.1511 14.2266
14 1.2 0.3224 0.8300 0.0028 -729.7235 6.7144
15 1.2 0.2927 0.8227 0.0026 -481.0421 4.4262
16 1.2 0.2632 0.8164 0.0023 -412.6295 3.7967
17 1.2 0.2353 0.8107 0.0021 -369.9972 3.4045
18 1.2 0.2083 0.8053 0.0019 -336.2951 3.0944
19 1.2 0.1826 0.8002 0.0017 -304.1869 2.7989
20 1.2 0.1583 0.7955 0.0016 -279.8806 2.5753
21 1.2 0.1343 0.7910 0.0015 -262.3342 2.4138
22 1.2 0.1108 0.7867 0.0014 -246.1110 2.2645
23 1.2 0.0878 0.7825 0.0009 -191.3266 1.7605
24 1.2 0.0732 0.7794 0.0007 -144.0108 1.3251
25 1.2 0.0605 0.7770 0.0007 -124.7951 1.1483
26 1.2 0.0481 0.7748 0.0006 -143.4206 1.3197
27 1.2 0.0366 0.7729 0.0006 -99.8074 0.9184
28 1.2 0.0256 0.7843 0.0004 -89.8746 0.8270
29 1.2 0.0176 0.7828 0.0002 -54.5939 0.5023
30 1.2 0.0138 0.7819 0.0001 -30.9432 0.2847
31 1.2 0.0115 0.7815 0.0001 -11.4580 0.1054
32 1.2 0.0094 0.7811 0.0001 -8.7970 0.0809
33 1.2 0.0073 0.7808 0.0001 -8.2174 0.0756
34 1.2 0.0052 0.7804 0.0001 -8.2106 0.0755
35 1.2 0.0032 0.7800 0.0001 -7.5166 0.0692
36 1.5 0.0013 0.8212 0.0001 -8.1250 0.0744

Table 11.1: Mathematical Model Results

Detailed Design - Absorption Column 64

X - NO Conversion between trays; Fa - Nitric Acid formed on each tray (kmol/hr);

Energy - Energy to be removed from each tray (kJ/s); Water Flowrate - Amount of
Cooling/Chilled Water Required for each tray (kg/s)

Temp. for section below Tray 13 - 50◦ C - Cooled using cooling water

Temp. for section above Tray 13 - 10◦ C - Cooled using chilled water

Equations solved in each step:

Step 1 -

k1 tP 2 = (b − a)−2 [X(b − a)/(1 − X)b] − ln[(1 − X) − (aX/k1 )]

X - NO conversion
k1 - NO Oxidation reaction rate constant
t - Residence time of gas between trays
P - Operating Pressure
b - Mole fraction of oxygen in gas
2a - Mole fraction of NO in gas

Step 2 -

p2N O2 [(2 − µ)2 + ABµ] + pN O2 [A(2 − µ) − ABP µ] + AP µ[2BP µ − (2 − µ)] = 0

pNO2 - NO2 Partial Pressure

µ - Ratio of moles of nitrogen peroxide to total moles of gas
P - Operating Pressure
A, B - Reaction constants for NO2 -N2 O4 equilibrium, given by k2 = A(1 - B*pNOX )

Step 3 -

Fa = [PN O + PN OX − (k3 E 3 + 2E 2 )/(k2 + E)](GN O + GN OX )C(PN O + PN OX )−1

Fa - Moles of nitric acid formed

PNO - Partial Pressure of NO
PNOX - Partial Pressure of NOX
E - Equilibrium partial pressure of NO2
k4 - Equilibrium relation between NO and N2 O4 - Thiemann et. al. [6]
k2 - Equilibrium relation between NO2 and N2 O4
k3 = k4 /k2 ; GNO - Flow rate of NO ; GNOX - Flow rate of NOX ; C - Tray Efficiency
Detailed Design - Absorption Column 65

11.2 Tray Selection and Specifications

The following parameters were considered while selecting the type of tray for the column:

Tray Type Bubble cap Dual Flow Sieve Valve

Capacity Moderate Very High High High
Pressure Low to Low to
High Moderate
Drop Moderate Moderate
Approx Approx
Turndown Very High Low
2:1 3-5:1
Efficiency 0.6-0.8 0.5-0.7 0.7-0.9 0.7-0.9
Relatively Low to
Maintenance Low Low
High Moderate
Fouling Low to
High Extremely low Low
Tendency Moderate
Marginally higher
Cost High Low Low
than sieve trays

Table 11.2: Tray Selection Parameters

Sieve Trays were finally selected because of versatile properties, making feasible for
almost every condition.

Plate Design Procedure provided in Sinnott et. al. [18] is used for our design. Sieve
Trays of the following specifications are used in the absorption column:

Column Diameter, Dc = 4m
Area, Ac = 12.57 m2
Downcomer Area, Ad = 0.12 Ac = 1.51 m2
Net Area, An = Ac - Ad = 11.06 m2
Active Area, Aa = Ac - 2Ad = 9.55 m2
Hole Area, Ah = 0.1Aa = 0.955 m2

Referring to Sinnott et. al. [18], we get lw /Dc = 0.77 for given hole area, hence
Weir Length, lw = 0.77Dc = 3.08 m
Weir height = 50 mm
Detailed Design - Absorption Column 66

Hole Diameter = 5mm

Plate Thickness = 5mm

11.2.1 Weeping Check

Maximum liquid flow rate = 17.83 kg/s

Minimum liquid flow rate, at 70% turn down = 12.48 kg/s
hw = 50 mm liquid
Maximum how = 750(17.83/(1325*3.08))2/3 = 20.05 mm liquid
Minimum how = 750(12.48/(1325*3.08))2/3 = 15.80 mm liquid
Hence, at minimum rate , hw + how = 65.80 mm liquid

Referring to Sinnott et. al. [18], we get K2 = 30.2 for given hw + how , hence
Uh,min = (30.5 - 0.9(25.4 - 5))/(13.27)0.5 = 3.25 m/s
Actual minimum vapour velocity = 3.333 m/s

So, the minimum operating rate will be above the weep point.

11.2.2 Plate Pressure Drop

Maximum vapour velocity, Uh,max = 3.87 m/s

Referring to Sinnott et. al. [18], we get Co = 0.84 for given hole area and plate thickness,
hence
Dry plate drop, hd = 51*(3.87/0.84)2 *(13.27/1325) = 10.84 mm liquid
Residual head, hr = 12500/1325 = 9.43 mm liquid

So, total plate pressure drop, ht = 10.84 + 9.43 + 50 + 20.05 = 90.32 mm liquid =
1.174 kPa

11.2.3 Perforated Area and Hole Pitch

Referring to Sinnott et. al. [18], we get θc = 102◦ for given hole area and plate thickness,
hence,
Angle subtended at plate edge by unperforated strip = 180 - 102 = 78◦
Detailed Design - Absorption Column 67

Mean length, unperforated edge strips = (4 - 0.05)*π*78/180 = 5.38 m

Area of unperforated edge strips = 0.05*5.38 = 0.269 m2
Mean length of calming zone = (4 - 0.05)*sin(102/2) = 3.07 m
Area of calming zone = 2(3.07*0.05) = 0.307 m2

Total area of perforations, Ap = 9.55 - 0.269 - 0.307 = 8.974 m2

Ah /Ap = 0.106, hence, referring to Sinnott et. al. [18], we get,
lp /dh = 3 for given hole area and perforated area, hence,
Hole pitch, lp = 15 mm, equilateral triangular.

11.2.4 Number of Holes

Area of one hole = 1.964 * 10-5 m2

Hence, number of holes = 0.955/(1.964 * 10-5) = 48,650

Type of Tray Sieve Tray

Flow type Cross Flow
Diameter (Dc ) 4m
Area (Ac ) 12.57 m2
Downcomer Area (Ad ) 1.51 m2
Net Area (An ) 11.06 m2
Active Area (Aa ) 9.55 m2
Hole Area (Ah ) 0.955 m2
Hole diameter 5 mm
Active Holes 48600
Weir Height 50 mm
Weir Length ( = 0.77Dc ) 3.08 m
MoC SS 304L (Nitric Acid Grade)
Plate thickness 5 mm
Plate Pressure Drop 1.175 kPa
Hole pitch Equilateral Triangular - lp = 15 mm
Turn Down 70% of Max Liquid Flow Rate
Liquid Hold up on tray 50 mm

Table 11.3: Final Tray Specifications

Detailed Design - Absorption Column 68

Figure 11.1: Sieve Tray Perforated Area with Downcomer

Figure 11.2: Sieve Tray Cooling Coils, Image provided by Krupp Uhde [13]

Pipe Diameter - 2 - 4 inches

Pipe Length on each tray - 10m
Process fluid - Cooling and Chilled water
Instead of the staggered arrangement, a packed single layer arrangement is used in the
Dual Pressure Nitric Acid Absorption Column, with each layer of cooling coils, instead
of being stacked over each other are packed in one layer, one after the other horizontally.
Detailed Design - Absorption Column 69

11.3 Head Selection

Head type Pressure range

Torispherical Upto 150 psig
Ellipsoidal 150 - 500 psig
Hemispherical Greater than 500 psig

11.4 Tower Thickness

The column is an internal pressure vessel, with cylindrical body and ellipsoidal heads.

Design Pressure, P = 12.1 bar

Internal Diameter, Di = 4 m
Sa , for SS304L = 180 MPa
Weld joint efficiency, E = 0.9
Corrosion allowance, c = 1mm
Milling tolerance, m =12.5%

Cylindrical Body -

P Di
t=
2[Sa E − 0.6P ]

Hence, we get, t = 15 mm and subsequently, trec = 18.29 mm

Volume of MoC used = π*Di *height*trec = 10.013 m3
Density = 8000 kg/m3
Hence, Weight of Shell = 80,103.2 kg

Ellipsoidal Heads -

P Di
t=
2[Sa E − 0.1P ]

Hence, we get t = 14.95 mm and subsequently, trec = 18.23 mm

Volume of MoC used = Ellipsoid Surface Area*trec = 0.393 m3
Weight of Head = 3141.04 kg

Skirt and Wind Considerations - MoC - CS

Column height = 44.6 m
Skirt height = 3.4 m
Detailed Design - Absorption Column 70

Insulation diameter = 5 m
Area = 240 m2
Wind velocity = 70.4 mph
Pw = 0.002*70.42 = 9.905 psf = 474.25 Pa
Force = Pw * G * Area = 474.25 * 1.9 * 240 = 216.3 kN

M = 216.3 * 1000 * (48/2) = 5190.2 kNm

Thickness, t = 2.296 mm and subsequently, trec = 3.767 mm

Column Height 44.6 m

Column Diameter 4m
Tray Type Sieve Tray
Number of trays 36
Tray Spacing Trays 0 - 12: 1m, Trays 13 - 35: 1.2 m
Tray 0 - NO Gas
Tray 35 - Process Water
Inlets Tray 12 - Acid Condensate
Trays 0-12 - Cooling Water
Trays 13-35 - Chilled Water
Body Thickness 18.29 mm
Head Type Ellipsoidal - Axis Ratio = 1.56:2
Head Thickness 18.23 mm
MoC SS 304L (Nitric Acid Grade)
Operating Pressure 11 barg
Operating Temperature 10-50◦ C
Design Pressure 12.1 barg
Design Temperature 65◦ C
Bottom and Top Disengaging spaces 1.5 m each

Table 11.4: Final Column Specifications

A Detailed Mechanical Drawing of the Absorption Column, with all design specifications
is available in Appendix C
Chapter 12

Environmental Impact

Only one waste stream exits our plant - Tail Gas containing pollutants NO and NO2 ,
widely known to be precursors to acid rain and smog, and greenhouse gas N2 O, having
a global warming potential 280 times that of CO2 . Though there is no statutory limit
on N2 O emissions in India, United Nation’s Clean Development Mechanism provides
monetary benefits for reducing N2 O emissions. NOX have a strict limit to be followed
for Nitric Acid Plants in India, and we require an abatement unit to take care of reducing
these emissions.

12.1 Tail Gas Composition and Emission Limits

The table below shows the composition of the Tail Gas leaving the Absorption Column:

Component Flow rate (kg/hr) Concentration

O2 3307 2.21 wt%
N2 145812 97.71 wt%
N2 O 142 1194.8 ppmv
NO2 18
637.8 ppmv
NO 58
Flow Rate 149337 kg/hr 118846 Nm3 /hr

Table 12.1: Composition of Tail Gas leaving Absorption Column

71
Environmental Impact 72

According to the data from the Ministry of Environment, Forest and Climate Change of
the Central Government of India [19], the permissible emission levels of NOX for Nitric
Acid Plants is 400 mg/m3 or 400ppmv. Since our NOX emissions are over the limit, we
will require an abatement unit to reduce the NOX levels.

12.2 Abatement Technology

EnviNOX R by Uhde GmbH is world’s best abatement technology for Nitric Acid Plants.
The EnviNOX R Unit provides >97% NOX and >98% N2 O removal, ensuring minimal
pressure drop (<40 mbar), for an average period of more than 10 years.

Referring Groves et. al. [20], many process variants of this technology are available, but
we will be using the EnviNOX R process variant - 2 for our nitric acid plant. The rea-
sons for choosing this is the lower reducing agent costs and lower reaction temperature
requirements for achieving very high emission reductions. Catalysts used in this tech-
nology, EnviCat R -NOX and EnviCat R -N2 O, are both Iron Zeolites, used individually
in the DeNOX and DeN2 O R stages.

Being a propreitary technology, Uhde has given exclusive rights to Clariant and Süd
Chemie for production of these catalysts for the vast nitric acid process market.

EnviNOX R process variant - 2 involves preheating the tail gas using the secondary air
and the reactor outlet gas stream to a temperature of 350◦ C at 12 bar. Stoichiometric
amounts of gaseous ammonia are mixed with the tail gas before entering the reactor
unit containing the catalyst pellets in an annular porous cylindrical setup. Ammonia
reduces NOX in the DeNOX stage of the reactor unit, ensuring that the DeN2 O R process
downstream doesn’t get hampered by the presence of NOX in the tail gas. Propane is
added to this mixture, which acts as a reducing agent for N2 O in the DeN2 O R stage,
removing >98% N2 O from the tail gas, giving us vastly reduced emissions for our plant.
The tail gas can is then expanded in the tail gas turbine. The tail gas turbine provides
around 65% of the power required to run the compressors.

DeNOX Reactions:
6N O2 + 8N H3 → 7N2 + 12H2 O

4N O + 4N H3 + O2 → 4N2 + 6H2 O
Environmental Impact 73

DeN2 O R Reactions:
10N2 O + C3 H8 → 10N2 + 3CO2 + 4H2 O

Figure 12.1: EnviNOX R Process Variant - 2, recreated from [20]

12.3 Tail Gas Post Abatement

A catalyst volume of 7m3 is used, as suggested Krupp Uhde [13]. This volume of catalyst
gives us a N2 O removal of 98.5% and NOX removal of 97%. The final tail gas composition
is shown in the table below:

Component Flow rate (kg/hr) Concentration

O2 3292 2.2 wt%
N2 145966 97.7 wt%
N2 O 2.13 18 ppm
NO2 0.54 5 ppmv
NO 1.74 15 ppmv
CO2 42 339 ppmv
H2 O 87 730 ppmv
Total 149392 kg/hr 119144 Nm3 /hr
Environmental Impact 74

12.4 Revised Plant Economics

Addition of the EnviNOX R Unit in the plant will incur increased fixed and working
capital investments, mainly involving the catalyst, additional ammonia and propane
costs.

12.4.1 Reactor Unit Cost

According to the data provided by Krupp Uhde [13],

Catalyst cost = A
C100,000 per m3 of catalyst
Since the catalyst is has an average life of 10 years, only one batch of catalyst is capi-
talised and the amount catalyst used is 7 m3 , hence, using A
C1 = INR 78,

Total Catalyst Cost = A

C100,000 * 7 = A
C700,000 = INR 5.46 Crores

The reactor is an annular cylindrical fixed bed reactor, with two catalyst bed of around
3.5 m3 each, filled inside a perforated cylinder, to allow gas flow from outside the cylinder
to the inner annular region. The beds are housed inside a cylindrical shell of 5 m
internal diameter, with ellipsoidal heads, operating at 12 bar. The MoC used is SS 321.
According to the data provided by Krupp Uhde [13], the reactor setup is designed by
Uhde GmbH and will cost around INR 1 Crore for the given catalyst volume. Hence,

Additional Fixed Capital Investment = INR 6.46 Crore

12.4.2 Additional Raw Material Costs

Additional Ammonia costs were included in the Raw Material Cost Estimation done in
Chapter 10

Additional Ammonia Required = 40 kg/hr

Propane Required = 15 kg/hr = 8.09 gallon/hr = 64,073 gallon/year Propane Cost =
INR 50/gal

Total Propane costs per year = INR 32,03,690 / year = $ 45,767 / year

Using the method outlined in Chapter 10, calculation were again done, giving us,
Environmental Impact 75

New Total Capital Investment = INR 923.99 Crores

New Raw Material Cost = $ 42.28 Million / year
New Total Product Cost = $ 122.18 Million / year = INR 855.26 Crores / year

12.4.3 Additional Revenue Calculation

Addition of a N2 O abatement technology can be registered under the United Nation’s

Clean Development Mechanism as a Large Scale Emission Reducing Project. Under the
CDM, in developing countries, efforts taken to reduce potential global warming causing
emissions are rewarded with Certified Emission Reduction units, or Carbon Credits,
that can be purchased by Annex I countries1 to comply with their emission limitation
targets as set by the Kyoto Protocol2 .

Since the prices of CERs fluctuate from year to year, two calculations were done for
calculating the payback period, (1) without the CER Revenue, and (2) with the CER
Revenue.

12.4.3.1 No CER Revenue

Total Revenue remains the same, hence we have,

Total Capital Investment = INR 921.29 Crores

Total Depreciable FCI = INR 697.80 Crores

Total Depreciation per year = INR 69.780 Crores / year

Taxation Rate, including surcharge and education cess = 28.3% = 0.283

Total Product Cost = $ 122.18 Million = INR 855.26 Crores / year

Revenue = $ 141.82 Million = INR 992.74 Crores / year

Bank Interest Rate = 6

Gross Profit = Revenue - Total Product Cost - Depreciation per year

= INR 67.700 Crores
1
Annex I countries - https://en.wikipedia.org/wiki/United_Nations_Framework_Convention_
on_Climate_Change#Annex_I_countries
2
Kyoto Protocol - https://en.wikipedia.org/wiki/Kyoto_Protocol
Environmental Impact 76

Net Profit = Gross Profit * (1 - Taxation Rate) = INR 48.452 Crores

Interest on TCI = Bank Interest Rate * TCI = INR 55.278 Crores

Hence, Payback Period = 7.6 Years

12.4.3.2 With CER Revenue

According to the UN’s Clean Development Mechanism, project registered under it will
be rewarded with 1 CER / tonne CO2 eq. reduced below the baseline for the entirety of
the crediting period. The baseline model was selected to be the emission from the plant,
as India doesn’t have any limits on N2 O emissions. The baseline model was selected
after referring to Methodology AM0028 [21], accessible from the CDM portal of UN.

Crediting Period = 10 years

Global Warming Potential(GWP) of N2 O = 280 * GWP of CO2

Emission Reduction = (142 - 2.13)*8000 = 1119 tonnes N2 O = 3,12,973 tonnes CO2 eq.

Trading value of CER = A

C0.26 / CER3 (Assuming trading value to remain constant)

Revenue Earned per year = A

C81,373 = INR 63.48 Lakhs / year

Hence, Revenue earned during Crediting Period = INR 6.348 Crores

Hence, the revenue earned from CER trading, will help us recover the fixed capital
investment required for setting up the abatement unit.

Payback Period = 7.6 years

3
https://www.moneycontrol.com/commodity/cer-price.html
Appendix A

Final Process Flow Diagram

The Final Process Flow Diagram with the Stream Table is shown below. The collective
image was taken using Google Spreadsheets. The PFD was made using draw.io.

77
 Line No 1 1C 1D 2 2A 3 4 5 6 7 8 8A 9 10 11 12 13 14 15 16 17 18 19
Stream Comp. Air feed Primary Air Secondary Air Ammonia Feed Evaporated NH3 Reactor Inlet Reactor Outlet HE102 Outlet HE103 Outlet Acid Condensate NOx Comp. inlet NOx Comp. Outlet Absorption Inlet Tail Gas Absorption Outlet Process Water Bleaching Air Nitric Acid Pdt Mixed Tail Gas Reduced Tail Gas Tail Gas Out Reducing Ammonia Propane
Phase g g g l g g g g g l g g g g l l g l g g g g g
NH3 0.00 0.00 0.00 11003.30 10963.30 10963.30 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 40.00 0.00 0.00 40.48 0.00
O2 43518.85 39004.55 4514.30 0.00 0.00 39004.55 13569.84 12125.47 9855.66 0.00 8590.66 8590.66 7042.89 3306.59 0.00 0.00 4514.30 0.00 3306.59 3291.59 3291.59 0.00 0.00
N2 145541.03 128386.69 17154.34 0.00 0.00 128386.69 128657.55 128657.84 128657.84 0.00 145812.18 145812.18 145812.18 145812.18 0.00 0.00 17154.34 0.00 145812.18 145966.09 145966.09 0.00 0.00
H2O 0.00 0.00 0.00 0.00 0.00 0.00 17412.30 17412.30 17412.30 16019.32 0.00 0.00 0.00 0.00 23815.84 11986.72 0.00 23815.84 0.00 87.18 87.18 0.00 0.00
N2O 0.00 0.00 0.00 0.00 0.00 0.00 141.88 141.88 141.88 0.00 141.88 141.88 141.88 141.88 0.00 0.00 0.00 0.00 141.88 2.13 2.13 0.00 0.00
NO2 0.00 0.00 0.00 0.00 0.00 0.00 0.00 4153.16 10679.54 0.00 18932.46 18932.46 23382.28 17.75 2319.83 0.00 2319.83 0.00 17.75 0.54 0.54 0.00 0.00
NO 0.00 0.00 0.00 0.00 0.00 0.00 18573.12 15864.54 11608.20 0.00 3095.52 3095.52 193.47 58.05 0.00 0.00 0.00 0.00 58.05 1.74 1.74 0.00 0.00
HNO3 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 9750.89 0.00 0.00 0.00 0.00 38857.50 0.00 0.00 38857.50 0.00 0.00 0.00 0.00 0.00
CO2 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 41.96 41.96 0.00 0.00
C3H8 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 15.00
Total 189059.88 167391.24 21668.64 11003.30 10963.30 178354.54 178354.69 178355.18 178355.42 25770.20 176572.69 176572.69 176572.69 149336.44 64993.17 11986.72 23988.47 62673.34 149376.44 149391.23 149391.23 40.48 15.00
Pressure (bar) 1.00 5.00 5.00 1.00 5.00 5.00 5.00 5.00 5.00 12.00 5.00 12.00 12.00 12.00 12.00 12.00 5.00 5.00 12.00 12.00 1.00 12.00 12.00
Temperature (C) 35.00 240.00 240.00 -33.00 70.00 230.00 427.00 300.00 185.00 50.00 50.00 260.00 50.00 130.00 50.00 10.00 80.00 50.00 350.00 350.00 35.00 350.00 350.00
 Appendix B

MATLAB Code for the

Mathematical Model for NOX
Absorption

AbsorptionColumn.m File
1 clear all ;
2 clc ;
3 X1 = fsolve ( @myfunc , 0.5) ;
4 Gno2 = fsolve ( @myfunc3 , 0.5) *1 . 4 8 7 3 9 1 84 1 / 1 2 ;
5 F = fsolve ( @myfunc2 , 0.5) ;
6 % Gno2 = fsolve ( @myfunc3 , 0.5) * 1 . 5 8 7 7 0 2 8 8 8 / 1 2 ;
7 % [ p1 , p2 , p3 ] = myfunc4 () ;
8 % p = [ p1 , p2 , p3 ];
9 % roots ( p ) * 1 . 5 5 2 5 7 3 2 0 2 / 1 2

Solving Step - 1
1 function [ y ] = myfunc ( x )
2
3 Vw = 1765 76.4/360 0;
4 G = 1.614361111;
5 b = 0 .061583 33333/ G ; % O2 molfrac
6 a = 0 . 0 0 1 8 0 5 5 5 5 5 5 6 / ( 2 * G ) ; % NO molfrac
7
8 T = 283;
9 P = 12;
10 rhov = P *100*( Vw / G ) /(8.314* T ) ;
11 k1 = (10^((635/ T ) - 1.0261) ) /(8.206* T *10^ -3) ;

79
 Environmental Impact 80

12 % k1 = exp ((530/ T ) + 7.78)

13 ar = pi *(4^2) /4;
14 vel = Vw /( rhov * ar ) ;
15 t = 1.5/ vel ;
16
17 y = (( x *( b - a ) /( b *(1 - x ) ) ) - log (1 - x -( a * x / k1 ) ) ) /(( b - a ) ^2) - k1 * t * P * P ;
18
19 end

Solving Step - 3
1 function [ y ] = myfunc2 ( f )
2
3 X = 0.7804;
4 P = 12;
5 T = 307.68;
6
7 V = 152108.312/3600;
8 Gno = 0 . 0 0 0 0 1 4 1 8 7 0 0 9 6 8 ;
9 Gno2 = 0.0041;
10 Gn2o4 = 0 . 00 65 10 5 81 49 5;
11 Gnox = Gno2 + Gn2o4 ;
12 G = 1.487318477;
13 Ghno3 = 0.000 2849531 8;
14 Gh2o = 0.1785554731;
15
16 Pno = P * Gno / G ;
17 Pno2 = P * Gno2 / G ;
18 Pn2o4 = P * Gn2o4 / G ;
19 Pnox = Pno2 + Pn2o4 ;
20
21 A = 10^(8.756 - (2838/ T ) ) ;
22 B = ( T /210.3) + (790/ T ) - (3.8794) ;
23 k2 = A *(1 - B * Pnox ) ;
24 w = ( Ghno3 *63) /( Ghno3 *63 + Gh2o *18) ;
25 rhol = ( Ghno3 *63 + Gh2o *18) /(( Ghno3 *63/1513) + ( Gh2o *18/1000) ) ;
26 nHNO3 = ( Ghno3 *63) /(( Ghno3 *63 + Gh2o *18) *10/ rhol ) ;
27 k4 = 10^(7.412 - 20.28921* w + 32.47322* w * w - 30.87* w * w * w ) ;
28 k3 = k4 / k2 ;
29 function [ f ] = myfunc5 ( x )
30 f = 3* k3 * x * x * x + (2* x * x / k2 ) + x - 3* Pno - Pnox ;
31 end
32 E = fsolve ( @myfunc5 , 0.5) ;
33 rhov = P *100*( V / G ) /(8.314* T ) ;
34 H = 0.04;
35 nNONOx = ( Gno *30 + Gno2 *46 + Gn2o4 *92) /(10* V /( rhov ) ) ;
36 R = ( Pno + Pnox ) / P ;
37 if R < 0.01
 Environmental Impact 81

38 A = 10.86 - 1.65*( R ^970000) + 37.59* exp ( -28.8* R ) ;

39 else
40 A = 8.73;
41 end
42 ar = pi *(4^2) /4;
43 vel = V /( rhov * ar ) ;
44 Dh = 0.003;
45 s = 0.9;
46 C = ( A *( P ^0.15) *( nNONOx ^0.1) *( X ^0.4) *( H ^0.15) *(( nHNO3 ) ^0.1) ) /(( vel ^0.26) *( Dh
^0.15) *( T ^0.87) *( s ^0.13) ) ;
47 y = (( Pno + Pnox - (( k3 * E * E * E + 2* E * E ) /( k2 + E ) ) ) *( Gno + Gnox ) * C /( Pno + Pnox )
) - f;
48
49 end

Solving Step - 2 and 4

1 function [ y ] = myfunc3 ( x )
2
3 T = 280;
4 A = 10^(8.756 - (2838/ T ) ) ;
5 B = ( T /210.3) + (790/ T ) - (3.8794) ;
6
7 Gno2 = 0. 00 4 15 07 91 5 82 ;
8 Gn2o4 = 0 . 00 65 50 1 49 65 3;
9 G = 1.487441445;
10
11 u = ( Gno2 + Gn2o4 ) / G ;
12 P = 12;
13
14 % y = (((( Gno2 -2* x ) ^2) * P ) /(( Gn2o4 + x ) * (G - x ) ) ) - A *(1 - B *(( Gno2 + Gn2o4 - x
) * P /( G - x ) ) ) ;
15 y = x * x *(((2 - u ) ^2) + A * B * u ) + x *( A *(2 - u ) - A * B * P * u *(2 - u ) ) + ( A * P * u *(2* B * P * u -
(2 - u ) ) ) ;
16
17 end
Appendix C

Detailed Drawing of Absorption

Column

The detailed drawing for the Absorption Column was made using Adobe Illustrator.
The detailed calculations to arrive at the dimensions have been shown in Chapter 11.

82
 4m
Tail Gas to HE106 Tail Gas to HE106

N105

1.56 m
Demister
Material of Construction
1.5 m
Cooling Coils N104
Process Water Inlet
For the column : SS304L (Nitric Acid Grade)
N069/N070
For the skirt : CS
PLATE 35

1.2 m Manhole 7
N067/N068

PLATE 34
Operating Parameters
N065/N066

PLATE 33
Operating Pressure - 11 barg
N063/N064 Operating Temperature - 283-323 K
PLATE 32 Weak Acid Feed (Plate 12) - 25770 kg/hr
N061/N062
Process Water Feed (Plate 35) - 11580 kg/hr
PLATE 31 NO Gas feed (Column Bottom) - 176577 kg/hr

N059/N060

PLATE 30

N057/N058 Design Parameters

PLATE 29

Manhole 6 Design Pressure - 12.1 barg

N055/N056

PLATE 28 Design Temperature - 338 K

Weld Joint Efficiency - 90%
N053/N054 Shell Thickness - 18.3 mm
PLATE 27
Head Thickness - 18.3 mm
N051/N052
Skirt Thickness - 3.8 mm
PLATE 26

N049/N050

PLATE 25

N047/N048
Nozzle Details
PLATE 24

Cooling Coils
N045/N046

PLATE 23
1) N001-N024, N071-N072 - Cooling Water Cooled coils
- Diameter : 2-4 inches
Manhole 5
N043/N044 2) N025-N070 - Chilled Water Cooled coils
PLATE 22 - Diameter : 2 inches
N041/N042

PLATE 21 Main Process Streams

3) N101 - NO Gas Inlet
N039/N040
- Diameter : 8 inches
PLATE 20
4) N102 - Product acid oulet
N037/N038
- Diameter : 6 inches
PLATE 19 5) N103 - Weak Acid Inlet
44.16 m - Diameter : 4 inches
6) N104 - Process Water Inlet
N035/N036

PLATE 18
- Diameter : 4 inches
N033/N034 7) N105 - Tail Gas Outlet
PLATE 17
- Diameter : 8 inches
Manhole 4
N031/N032

PLATE 16 Manholes
8) Manhole 1-Manhole 7 - Diameter: 0.6 m
N029/N030

PLATE 15

N027/N028

PLATE 14

N025/N026
Design Notes
PLATE 13
N103
1.2 m Weak Acid Inlet 1) Distance between the plates : Plate 0 to Plate 12 - 1 m
PLATE 12
N023/N024
Plate 12 to Plate 35 - 1.2 m
1m 2) Fillet weld joining column cylinder to ellipsoidal heads
N021/N022

PLATE 11
3) Stainless Steel plate is used to join the skirt and the column
Manhole 3
4) Exact representation of manhole and pipe positions is as in figure 2
PLATE 10
N019/N020
5) For figure 1, cooling coils are not diametrically opposite for consecutive
trays, they are represented as such for ease of viewing.
N017/N018

PLATE 9

N015/N016

PLATE 8

N013/N014

PLATE 7

N011/N012

PLATE 6

N009/N010

PLATE 5
Manhole 2
N007/N008

PLATE 4

N005/N006

PLATE 3

N003/N004

PLATE 2

N001/N002

PLATE 1
1m
N071/N072

PLATE 0
1.5 m NOX
N101 Gas
NOX Gas Inlet Inlet

0.44 m

1.56 m
Process Water Inlet
4.5 m
Weak Acid Inlet
N102
Product Acid Outlet
Product Acid Outlet Cooling/Chilled Water Inlet

1.8 m
0.6 m
Manhole 1
References

[1] Thyssenkrupp Industrial Solutions Nitric Acid Process Handbook -

https://d13qmi8c46i38w.cloudfront.net/media/UCPthyssenkruppBAIS/
assets.files/products___services/fertilizer_plants/nitrate_plants/
brochure-nitric-acid_scr.pdf

[2] Global Nitric Acid Market By Plant Type, By Sales Channel, By Application, By
Region, Competition Forecast and Opportunities, 2011-2025, Research and Markets
Nitric Acid Sample Market Report -
https://www.researchandmarkets.com/research/qsn6h4/global_nitric

[3] Nitric Acid Market Size, Share & Trends Analysis Report By Application (Fertilizers,
Adipic Acid, Nitrobenzene, Toulene di-isocynate, Nitrochlorobenzene), By Region,
Vendor Landscape, And Segment Forecasts, 2012-2022, Grand View Research Nitric
Acid Sample Market Report -
www.grandviewresearch.com/industry-analysis/nitric-acid-market

[4] Nitric Acid IHS Chemical Economics Handbook -

www.ihsmarkit.com/products/nitric-acid-chemical-economics-handbook.
html

[5] Jacob A. Moulijn, Michiel Makkee, Annelies E. Van Diepen, Chemical Process
Technology, p.260-267, 2nd ed., 2013, John Wiley & Sons Ltd., Great Britain

[6] Thiemann M, Scheibler E, Wiegand KW, Nitric acid, nitrous acid, and nitrogen
oxides, Ullmann’s Encyclopedia of Industrial Chemistry, Vol. 23, Wiley–VCH
Verlag GmbH & Co. KGaA, 2003. doi:10.1002/14356007.a17 293

[7] Deepak Fertilisers and Petrochemicals Corporation Ltd., MIDC Road, Taloja, Navi
Mumbai, Maharashtra - 410208, India

84
References 85

[8] Martyn S. Ray (Curtin University of Technology, Western Australia), David

W. Johnston (Shell Refining(Australia) Pvt. Ltd.), Chemical Engineering Design
Project: A Case Study Approach, Topics in Chemical Engineering, ISSN: 0277-
5883, Vol. 6, Gordon and Breach Science Publishers, 1989, United Kingdom
http://inspect.nigc.ir/Portal/Images/Images_Traning/files/files/
chemist%20book/Chemical%20Engineering%20Design%20Project%20-%20A%
20Case%20Study%20Approach.PDF

[9] Hirokazu Tsukahara,Takanobu Ishida, Mitsufumi Mayumi, Gas-Phase Oxidation of

Nitric Oxide: Chemical Kinetics and Rate Constant, Nitric Oxide, Vol. 3 - Issue
3, Elsevier, 1999, Japan. doi:10.1006/niox.1999.0232

[10] Max S. Peters, Klaus D. Timmerhaus, Plant Design And Economics For
Chemical Engineers, 4th ed., ISBN - 0-07-100871-3, McGraw Hill Inc., Inter-
national Edition, 1991, United States

[11] Stanley M. Walas, Chemical Process Equipment Selection and Design, But-
terworth - Heinemann Series in Chemical Engineering, ISBN - 0-7506-9385-1, But-
terworth - Heinemann, Reed Publishing, 1990, United States

[12] The Chemical Engineering Cost Index, Chemical Engineering Online -

https://www.chemengonline.com/pci

[13] Mr. Amrish Dholakia, Engineering Manager & General Manager-Process, Uhde
House, Thyssenkrupp Industrial Solutions (formerly Uhde India), Vikhroli, Mumbai
- 400083

[14] Gold Price India Website - https://www.goldpriceindia.com

[15] Infomine - http://www.infomine.com/investment/metal-prices/rhodium/

[16] CL 407 - Process Equipment Design, Handouts and Reading Material by Prof. Arun
S. Moharir, Prof. Yogendra Shastri, Indian Institute of Technology Bombay, Mumbai
- 400076

[17] United Nations Industrial Development Organisation (UNIDO), Internation Fer-

tiliser Development Centre (IFDC), Fertilizer Manual, ISBN - 0-7923-5032-4,
Kluwer Academic Publishers, 1998, Netherlands
References 86

[18] R.K. Sinnott, J.M. Coulson, J.F. Richardson, Chemical Engineering Design,
Chemical Engineering, p.564-586, Vol. 6 3rd ed., ISBN - 0-7506-4142-8, But-
terworth - Heinemann, 1999, Great Britain

[19] G.S.R. 1607(E), Ministry of Environment, Forest and Climate Change, Central
Government of India, 29th December 2017
https://drive.google.com/open?id=1xkQjup6FQcv8fdppsAhLQLrq0oE6upVp

[20] Groves, M.C.E., Sasonow, A., Hydrogen and Nitrates Division, Uhde GmbH Uhde
EnviNOX R technology for NOX and N2 O abatement: a contribution to reducing
emissions from nitric acid plants, Journal of Integrative Environmental Sci-
ences, 7(sup1), p.211222, 2010, doi:10.1080/19438151003621334

[21] AM0028: N2 O destruction in the tail gas of Caprolactam production plants - Ver.
06.0, United Nations Framework Convention on Climate Change
https://cdm.unfccc.int/filestorage/b/g/
IV326LBA5XCTF04RUQ7MWDKG8SPNZ1.pdf/EB73_repan05_AM0028_ver06.0.pdf?t=
a2d8cHBxcm1ifDCgYNMsIPmIXChVn94xNxCI