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PLANT DESIGN FOR THE PRODUCTION OF

400,000 METRIC TONNES OF NITRIC ACID

PER ANNUM FROM AIR OXIDATION OF

AMMONIA GAS

BY 

ANDREW OFOEDU

DEPARTMENT OF CHEMICAL

ENGINEERING

FEDERAL UNIVERSITY OF TECHNOLOGY,

OWERRI.

SEPTEMBER 2013
 

EXECUTIVE SUMMARY 

 This report describes the detailed design of a plant to produce


400000 tonnes of nitric acid per year by Ostwald Process. The
single pressure process was selected as the most advantageous,
having considered several factors one of which is ecient energy
management. The process begins with the vapori!ation of 
ammonia at 1000 "Pa and #$%& using process heat. 'team is then
used to superheat the ammonia up to about (0%&. )iltered air is
compressed in an a*ial compressor to a discharge pressure of 
about +40"Pa and temperature of 1$$%&. Part of the air is
diverted for acid stripping. This preheated air and the ammonia
vapour are then mi*ed and passed through the platinumrhodium
catalyst gau!e in a converter for o*idation. The reaction gas -ows
through a series of heat e*changers for recovery of energy as
either highpressure superheated steam, or as shaft horsepower
from the e*pansion of hot tail gas in the turbine. &onsidering the
pro*imity to mar"et, sea port and source of raw materials, it was
decided to site the plant in /leme, ivers 'tate. The plants
 

estimated capital investment is $.41 billion. The rate of return


on investment is 23.2$ and the paybac" period is estimated to
be # years and + months. Thus, the pro5ect is both technically and
economically feasible.

TABLE OF CONTENT
 Title page i
/*ecutive
'ummaryii
 Table of 
contentiii

CHAPTER ONE
1.0 6ntroduction1
1.#
7esign
 5usti8cation#
1.4
7esign
Ob5ectives4
  CHAPTER TWO
2.0 9iterature
review$
2.1 :istory of ;itric acid
production$
2.2 <mmonia o*idation
chemistry(
 

2.# /mission and


&ontrol14
2.4 'tructure and
bonding1$
2.$
eactions
13
2.3
=ses
1>
2.+
'afety
21
2.( Pinch technology in modern
plant22
2.> Plant 9ocation 
24 2.>.$ Plant layout
2>
2.>.3 Process routes for the production of nitric acid
##

CHAPTER THREE

#.0 ?aterial balance 42

#.1 &onservation of mass 42

#.2 ?ethods of material balancing 4#

#.# ?aterials balance assumptions44

#.4 'ummary of material balance calculations44

#.$ ?aterial balance for each unit 44


 

CHAPTER FOUR
4.0 /nergy balance  $#
4.1 &onservation of energy $4
4.2 /nergy balance assumptions $3
4.# 'ummary for energy balances$3

CHAPTER FIVE
$.0 &hemical /ngineering
design31
$.1 Process units of ;itric acid
Production31

CHAPTER SIX

3.0 /@uipment design and speci8cation 33

3.1 Problem speci8cation3+

3.2 <naly!ing the problem solution3(

3.# Preliminary
design3(

3.4 ?aterial
'election3>

3.$ 7esign
optimi!ation3>

3.3 'ummary of design and e@uipment speci8cation


calculation+0

CHAPTER SEVEN

+.0 Process control and instrumentation+#


 

+.1
Ob5ective
+#

+.2 Plant control instrumentation+4

+.# <larms and safety trips ++

+.4 9ining, piping, valves and pumps +(

+.$ Pipe support (1

CHAPTER EIGHT

(.0 'afety and environmental


considerations(2

(.1
'afety
(2

(.2 :a!ard and Operability A:<BOPC


study(>

(.# /nvironmental impact


assessment>+

CHAPTER NINE

>.1 Overview10#

>.2 /conomic &onsideration10#

>.# &ost
estimation
103

>.3 /conomic analyses calculation10(


 

CHAPTER TEN

10.0 'tart up and shut down procedure11#

10.1 /mergency shut down and emergency depressuri!ation


114

10.2 ;oti8cation114

10.# ecord "eeping  11$

10.4 'tartup operation 113

CHAPTER ELEVEN

11.0 &onclusion
ecommendation11(

11.1
&onclusion
11(

11.2 ecommendation
11>

REFERENCES 120

APPENDIX I

 Tables and
&harts
12#

APPENDIX II
 

?aterial Dalance
&alculation123

APPENDIX III

/nergy Dalance
&alculation1#2

APPENDIX IV

/@uipment 7esign
&alculation1#+

APPENDIX V

/@uipment &osting
&alculation141
 

>

CHAPTER ONE
INTRODUCTION

1.1 BACKGROUND INFORMATION

;itric acid is a strong acid and a powerful o*idi!ing agent with


enormous possibilities for applications in the chemical processing
industry. 6t has commercial uses as a nitrating agent, o*idi!ing
agent, solvent, activating agent, catalyst and hydroly!ing agent.
6n relation to world production, appro*imately 3$ of all nitric
acid produced is used for the production of ammonium nitrate
Aspeci8cally for fertili!er manufactureC.
 

10

;itric acid is now produced commercially using the stepwise,


catalytic o*idation of ammonia with air, to obtain nitrogen
mono*ide and nitrogen dio*ide. These nitrogen o*ides are
subse@uently absorbed in water to yield between $0 and 3(
strength nitric acid by weight. )or applications re@uiring higher
strengths, several methods of concentrating the acid are used.

 The traditional methods areE

AaC /*tractive distillation with dehydrating agents such as


sulphuric acid or magnesium nitrateF

AbC eaction with additional nitrogen o*ides.

 The latter techni@ue has the greatest application in industry.

 The chemistry of ammonia o*idation is remar"ably simple with


only si* main reactions that need to be considered.

1.1.1 PROPERTIES AND USES

;itric acid is an o*idi!ing mineral acid with physical and chemical


properties that ma"e it one of the most useful inorganic minerals.
6t is a colorless li@uid at room temperature and atmospheric
pressure. 6t is soluble in water in all proportions and there is a
release of heat of solution upon dilution. 6ts high solubility in
water is the basis for the process methods used for commercial
nitric acid manufacture. 6t is a strong acid that almost completely
ioni!es when in dilute solution. 6t is also a powerful o*idi!ing
agent with the ability to passivate some metals such as iron and
 

11

aluminum. < compilation of many of the physical and chemical


properties of nitric acid are presented in the <ppendi*. <rguably
the most important physical property of nitric acid is its
a!eotropic point, this in-uences the techni@ues associated with
strong acid production. The constantboiling mi*ture occurs at
121.>%&, for a concentration of 3(.4AwtC acid at atmospheric
pressure.

;itric acid has enormously diverse applications in the chemical


industry. 6t has commercial uses as a nitrating agent, o*idi!ing
agent, solvent, activating agent, catalyst and hydroly!ing agent.
 The most important use is undoubtedly in the production of 
ammonium nitrate for the fertili!er and e*plosives industries,
which accounts for appro*imately 3$ of the world production of 
nitric acid.

;itric acid has a number of other industrial applications. 6t is used


for pic"ling stainless steels, steel re8ning, and in the manufacture
of dyes, plastics and synthetic 8bers. ?ost of the methods used
for the recovery of uranium, such ! ion e*change and solvent
e*traction, use nitric acid.

<n important point is that for most uses concerned with chemical
production, the acid must be concentrated above its a!eotropic
point to greater than >$AwtC. &onversely, the commercial
manufacture of ammonium nitrate uses nitric acid below its
a!eotropic point in the range $0 3$ Awt.C. 6f the stronger
 

12

chemical grade is to be produced, additional process e@uipment


appropriate to supera!eotropic distillation is re@uired.

 There is a potential health ha!ard when handling, and operating


with, nitric acid. ;itric acid is a corrosive li@uid that penetrates
and destroys the s"in and internal tissues. &ontact can cause
severe burns. The acid is a potential ha!ard, the various nitrogen
o*ides present as product intermediates in the process are also
to*ic. <n assessment of the health ris" must be fundamental to
the design of any process. )urther consideration and
recommendations for the operating health ris" and environmental
impact of the plant are presented in the <ppendi*.

1.2 DESIGN "USTIFICATION

<t present, there is no ;itric acid plant in ;igeria. The little ;itric
acid produced mainly by fertili!er plants in the country is used up
immediately by them to ma"e their fertili!er. This means that
most of the all ;itric acid used in the country is imported.

< ;itric acid plant sited in the country producing ;itric acid made
available to the ;igerian mar"et will not only reduce importation
of the acid but also encourage fertili!er production, create 5ob
opportunities as well as develop the area in which it is sited.

1.3 DESIGN OB"ECTIVES


 

1#

•  To design a plant that will deliver 400000 metric tonnes of 
30AwtC ;itric <cid per annum.
•  To determine the technical and economic feasibility of the
plant.

CHAPTER TWO
 

14

  LITERATURE REVIEW

2.1 HISTORY OF NITRIC ACID PRODUCTION

=ntil the beginning of the 20th century, ;itric acid A:;O #C, also
"nown as a@ua fortis and spirit of niter was prepared
commercially by reacting sulphuric acid with either potassium
nitrate AsaltpetreC or with sodium nitrate A&hile saltpetre or nitreC.
=p to four tonnes of the two ingredients were placed into large
retorts and heated over a furnace AGir" 1>>3C. The volatile
product vapouri!ed and was collected for distillation. <n acid of 
>#>$ A wtC was produced AHregory 1>>>C.

6n 1>0# the electricarc furnace superseded this primitive original


techni@ue. 6n the arc process, nitric acid was produced directly
from nitrogen and o*ygen by passing air through an electricarc
furnace Aay 1>>0C.

Hregory A1>>>, p.40C argues that I<lthough the process bene8tted


from an ine*haustible supply of free feed material AairC, the power
consumption for the arc furnace was cost prohibitive

<ccording to ay A1>(>, p.(C esearchers returned to the


o*idation of ammonia in air, Arecorded as early as 1+>(C in an
eJort to improve production economics. 6n 1>01 Kilhelm Ostwald
had 8rst achieved the catalytic o*idation of ammonia over a
platinum catalyst. The gaseous nitrogen o*ides produced could be
easily cooled and dissolved in water to produce a solution of nitric
 

1$

acid. This achievement began the search for an economic process


route.

Dy 1>0( the 8rst commercial facility for production of nitric acid,


using this new catalytic o*idation process, was commissioned
near Dochum in Hermany Aay et al 1>(>C. The :aberDosch
ammonia synthesis process came into operation in 1>1#, leading
to the continued development and assured future of the ammonia
o*idation process for the production of nitric acid. Aay et al 1>(>C

7uring Korld Kar 1, the intense demand for e*plosives and


synthetic dyestuJs created an e*pansion of the nitric acid
industry.

?any new plants were constructed, all of which employed the


ammonia o*idation process. This increased demand served as the
impetus for several brea"throughs in process technology.

 These includedE

AaC The development of chromesteel alloys for tower


construction, replacing the heavy stoneware and acidproof 
bric"s. This enabled process pressures above atmospheric levels
to be used.

AbC The improved design of feed preheaters enabled higher


process temperatures to be attained. :igher temperatures
improved the yields and capacities, and also reduced e@uipment
re@uirements AOhrue et al 1>>>C.
 

13

AcC /arly developments in automatic process control improved


process performance and reduced labor re@uirements.

<ll of these factors helped to improve the process eciency. The


increasing availability of ammonia reduced processing costs still
further.

6n the late 1>20s the development of stainless steels enabled


manufacturers to use higher operating pressures. The increase in
yield and lower capital re@uirements easily 5usti8ed the use of 
high pressure operation despite increased ammonia consumption.

 The introduction of higher pressure processes resulted in a


divergence of operating techni@ue within the industry. The =nited
'tates producers opted for a highpressure system, using a
constant high pressure throughout the process. The /uropean
manufacturers opted for a splitpressure system. This latter
system entails operating the ammonia o*idation section at
atmospheric pressure, while the absorption unit is operated at
higher pressures, thus capitali!ing on improved absorption rates.
A:arvin et al 1>+>C

ecent developments in the ammonia o*idation process have


included eJorts to reduce catalyst losses in the process. Platinum
recovery 8lters have been installed at various stages in the
process. AOhrue et al 1>>>C

Holdpalladium gau!e 8lter pads have been added on the e*it side
of the catalyst bed, inside the reactorconverter units. These
 

1+

8lters have reportedly ensured a platinum recovery of (0 A<non


1>+>C. <nother trend has been for the use of additional 8lters in
the downstream units. These 8lters are of aluminosilicate
construction.

Perhaps the greatest progress in nitric acid production technology


has been in the manufacture of strong nitric acid AL>0 by
weightC. <dvances in the areas of supera!eotropic distillation and
in high pressure absorption are most signi8cant. AOh"ubo et al
1>>>C

esearch wor" is continually being performed in an eJort to


reduce nitrogen o*ide emissions from nitric acid plants. The
:umphreys and HlasgowDolme nitric acid process is 5ust one
e*ample of a new philosophy being applied to the absorption
systems of wea" nitric acid plants A$03( by weightC. ;itrogen
o*ide emissions have been reduced from 2000$000 ppm to less
than 1000 ppm Aay et al 1>(>C.

)or the production of stronger nitric acid, tail gases are now being
treated by selective or nonselective catalytic combustion
systems. These innovative units have reduced the nitrogen o*ide
emissions to below 400 ppm Aay et al 1>(>C.

2.2 AMMONIA OXIDATION CHEMISTRY 

;otably, all commercial nitric acid production methods used today


are centered on the o*idation of ammonia. 6t is therefore
appropriate to investigate the chemistry of this process, in the
 

1(

"nowledge that it is directly applicable to any of the production


processes available. A&hilton 1>30C

 The chemistry of the o*idation of ammonia is surprisingly simple.


6t begins with a single pure compound, plus air and water, and
ends with another pure compound in a@ueous solution, with
essentially no byproducts. The process may be described by 5ust
si* ma5or reactions as shown as followsE

 N H 3( g) + 2 O2 → H N O3 (aq )+ H 2 O (l )


1.

2. 4 N H 3( g )+ 5 O2 ( g) → 4 N O( g )+ 6 H 2 O(l )


 

2 N O( g) + O2 → 2 N O 2 ( g)
#.

2 N O2 ( g) ⇌ N 2 O4
4.

3 N 2 O 4 + 2 H 2 O( l ) → 4 HN O 3 + 2 N O ( g)


$.  

3 N O2 ( g) + H 2 O( l ) → 2 HN O3 (aq )+ N O( g)


3.

eaction 1 is the overall reaction for the process. This net result is
achieved from three separate, and distinct, chemical steps. The
8rst is the o*idation of ammonia to nitrogen mono*ide Aeaction
2C. The second is the further o*idation of nitrogen mono*ide to
nitrogen dio*ide Aeaction #C, then nitrogen dio*ide to nitrogen
tetro*ide Aeaction 4C. The third and 8nal stage involves the
absorption of these nitrogenbased o*ides into water to form the
nitric acid product Aeactions $ and 3C. 6n most commercial
 

1>

processes, each of these three stages is conducted in separate


process units. A&hilton 1>30C

 The 8rst step in the process is the heterogeneous, highly


e*othermic, gasphase catalytic reaction of ammonia with o*ygen
Aeaction 2C. The primary o*idation of ammonia to nitric acid
Aover a catalyst gau!e of >El platinumrhodium alloyC proceeds
rapidly at process temperatures between >00>+0%&. AGent 1>(#C

 The second step in the process involves two reactions Aeactions


# and 4C. These are the o*idations of nitrogen mono*ide to the
dio*ide and tetro*ide forms. The e@uilibrium mi*ture is loosely
referred to as nitrogen pero*ide. Doth reactions are homogenous,
moderately e*othermic, gasphase catalytic reactions. <ll
reactions shown are highly e*othermic. A&hilton 1>30C

 The third step in the process involves cooling the reaction gases
below their dew point, so that a li@uid phase of wea" nitric acid is
formed. This step eJectively promotes the state of o*idation and
dimeri!ation Aeactions # and 4C, and removes water from the gas
phase. This in turn increases the partial pressure of the nitrogen
pero*ide component. A&hilton 1>30C

)inally, nitric acid is formed by the reaction of dissolved nitrogen


pero*ide with water Aeactions $ and 3C.

;itric acid is produced by 2 methods. The 8rst method utili!es


o*idation, condensation, and absorption to produce a wea" nitric
acid. Kea" nitric acid can have concentrations ranging from #0 to
 

20

+0 percent nitric acid. The second method combines dehydrating,


bleaching, condensing, and absorption to produce a highstrength
nitric acid from a wea" nitric acid. :ighstrength nitric acid
generally contains more than >0 percent nitric acid. The following
te*t provides more speci8c details for each of these processes.
A&hilton 1>30C
2.2.1 WEAK NITRIC ACID PRODUCTION
<ccording to ayA1>(>, ;early all the nitric acid produced in the
=. '. is manufactured by the hightemperature catalytic o*idation
of ammonia. This process typically consists of # stepsE A1C
ammonia o*idation, A2C nitric o*ide o*idation, and A#C absorption.
/ach step corresponds to a distinct chemical reaction.
1. AMMONIA OXIDATION
)irst, a 1E> ammoniaair mi*ture is o*idi!ed at a temperature of 
1#(0 to 14+00) as it passes through a catalytic convertor,
according to the following reactionE
4 N H 3 + 5 O2 → 4 NO + 6 H 2 O

 The most commonly used catalyst is made of >0 percent platinum


and 10 percent rhodium gau!e constructed from s@uares of 8ne
wire. =nder these conditions, the o*idation of ammonia to nitric
o*ide A;OC proceeds in an e*othermic reaction with a range of >#
to >( percent yield. O*idation temperatures can vary from 1#(0 O)
to 13$00). A&hilton 1>30C :igher catalyst temperatures increase
reaction selectivity toward ;O production. 9ower catalyst
temperatures tend to be more selective toward less useful
productsE nitrogen A;2C and nitrous o*ide A;2OC.
 

21

;itric o*ide is considered to be a criteria pollutant and nitrous


o*ide is "nown to be a global warming gas. The nitrogen
dio*idedimmer mi*ture then passes through a waste heat boiler
and a platinum 8lter. A&hilton 1>30C
2. NITRIC OXIDE OXIDATION
 The nitric o*ide formed during the ammonia o*idation must be
o*idi!ed. The process stream is passed through a
coolercondenser and cooled to 100 0) or less at pressures up to
113 pounds per s@uare inch absolute ApsiaC. The nitric o*ide
reacts noncatalytically with residual o*ygen to form nitrogen
dio*ide A;O2C and its li@uid dimmer, nitrogen tetrao*ideE
2 N O2 + O2 → 2 N O2 ⇌ N 2 O4

  This slow, homogeneous reaction is highly temperature and


pressure dependent. Operating at low temperatures and high
pressures promotes ma*imum production of ;O2  within a
minimum reaction time AGent 1>(#C.

#. ABSORPTION
 The 8nal step introduces the nitrogen dio*idedimmer mi*ture
into an absorption process after being cooled. The mi*ture is
pumped into the bottom of the absorption tower, while li@uid
dinitrogen tetrao*ide is added at a higher point. 7eioni!ed
process water enters the top of the column. Doth li@uids -ow
countercurrent to the nitrogen dio*idedimmer gas mi*ture.
O*idation ta"es place in the free space between the trays, while
absorption occurs on the trays. The absorption trays are usually
 

22

sieve or bubble cap trays. The e*othermic reaction occurs as


followsE
3 N O2 + H 2 O → 2 HN O3+ NO

< secondary air stream is introduced into the column to reo*idi!e


the ;O that is formed in eaction #. This secondary air also
removes ;O2 from the product acid. <n a@ueous solution of $$ to
3$ percent AtypicallyC nitric acid is withdrawn from the bottom of 
the tower. The acid concentration can vary from #0 to +0 percent
nitric acid. The acid concentration depends upon the temperature,
pressure, number of absorption stages, and concentration of 
nitrogen o*ides entering the absorber.

 There are 2 basic types of systems used to produce wea" nitric


acidE singlestage pressure process and dualstage pressure
process A:arvin et al 1>+>C. 6n the past, nitric acid plants have
been operated at a single pressure, ranging from atmospheric
pressure to 14.+ to 20# psia. :owever, since eaction 1 is favored
by low pressures and eactions 2 and # are favored by higher
pressures, newer plants tend to operate a dual stage pressure
system, incorporating a compressor between the ammonia
o*idi!er and the condenser. The o*idation reaction is carried out
at pressures from slightly negative to about $( psia, and the
absorption reactions are carried out at 113 to 20# psia. A:arvn et
al 1>+>C
6n the dualstage pressure system, the nitric acid formed in the
absorber AbottomsC is usually sent to an e*ternal bleacher where
air is used to remove AbleachC any dissolved o*ides of nitrogen.
 

2#

 The bleacher gases are then compressed and passed through the
absorber. The absorber tail gas AdistillateC is sent to an
entrainment separator for acid mist removal. ;e*t, the tail gas is
reheated in the ammonia o*idation heat e*changer to
appro*imately #>20). The 8nal step e*pands the gas in the power
recovery turbine. The thermal energy produced in this turbine can
be used to drive the compressor.
2.2.2 HIGH STRENGTH NITRIC ACID PRODUCTION
< highstrength nitric acid A>( to >> percent concentrationC can be
obtained by concentrating the wea" nitric acid A#0 to +0 percent
concentrationC using e*tractive distillation. A6mai et al 1>>>C The
wea" nitric acid cannot be concentrated by simple fractional
distillation. The distillation must be carried out in the presence of 
a dehydrating agent. &oncentrated sulfuric acid Atypically 30
percent sulfuric acidC is most commonly used for this purpose.
 The nitric acid concentration process consists of feeding strong
sulfuric acid and $$ to 3$ percent nitric acid to the top of a
pac"ed dehydrating column at appro*imately atmospheric
pressure. The acid mi*ture -ow downward, countercurrent to
ascending vapors. &oncentrated nitric acid leaves the top of the
column as >> percent vapor, containing a small amount of ;O 2
and o*ygen AO2C resulting from dissociation of nitric acid. The
concentrated acid vapor leaves the column and goes to a
bleacher and a countercurrent condenser system to eJect the
condensation of strong nitric acid and the separation of o*ygen
and o*ides of nitrogen A;O2C byproducts. AOh"ubo et al 1>>>C
 

24

 These byproducts then -ow to an absorption column where the


nitric o*ide mi*es with au*iliary air to form ;O2, which is
recovered as wea" nitric acid. 6nert and unreacted gases are
vented to the atmosphere from the top of the absorption column.
/missions from this process are relatively minor. < small absorber
can be used to recover ;O2. AGir" et al 1>(1C

2.3 EMISSIONS AND CONTROL


/missions from nitric acid manufacture consist primarily of ;O,
;O2 Awhich account for visible emissionsC, trace amounts of :;O#
mist, and ammonia A;: #C. Dy far, the ma5or source of nitrogen
o*ides A;O2C is the tailgas from the acid absorption tower. 6n
general, the @uantity of ;O2  emissions is directly related to the
"inetics of the nitric acid formation reaction and absorption tower
design. ;O2 emissions can increase when there is A1C insucient
air supply to the o*idi!er and absorber, A2C low pressure,
especially in the absorber, A#C high temperatures in the cooler
condenser and absorber, A4C production of an e*cessively high
strength product acid, A$C operation at high throughput rates, and
A3C faulty e@uipment such as compressors or pumps that lead to
lower pressures and lea"s, and decrease plant eciency. A9eray et
al 1>+>C
oudier A1>+>C states that the two most common techni@ues used
to control absorption tower tail gas emissions are e*tended
absorption and catalytic reduction. /*tended absorption reduces
 

2$

;O2 emissions by increasing the eciency of the e*isting process


absorption tower or incorporating an additional absorption tower.
<n eciency increase is achieved by increasing the number of 
absorber trays, operating the absorber at higher pressures, or
cooling the wea" acid li@uid in the absorber. The e*isting tower
can also be replaced with a single tower of a larger diameter
andor additional trays.
6n the catalytic reduction process Aoften termed catalytic
o*idation or incinerationC, tail gases from the absorption tower are
heated to ignition temperature, mi*ed with fuel Anatural gas,
hydrogen, propane, butane, naphtha, carbon mono*ide, or
ammoniaC and passed over a catalyst bed. 6n the presence of the
catalyst, the fuels are o*idi!ed and the ;O2 are reduced to ;2. The
e*tent of reduction of ;O2  and ;O to ;2  is a function of plant
design, fuel type, operating temperature and pressure. 'pace
velocity through the comparatively small amounts of nitrogen
o*ides is also lost from acid concentrating plants. These losses
Amostly ;O2C are from the condenser system, but the emissions
are small enough to be controlled easily by ine*pensive
absorbers. <cid mist emissions do not occur from the tailgas of a
properly operated plant. The small amounts that may be present
in the absorber e*it gas streams are removed by a separator or
collector prior to entering the catalytic reduction unit or e*pander.
AGent 1>(#C
 

23

 The acid production system and storage tan"s are the only
signi8cant sources of visible emissions at most nitric acid plants.
/missions from acid storage tan"s may occur during tan" 8lling.

2.4 STRUCTURE AND BONDING

)ig 2E Two ma5or resonance representations of :;O#.

 The molecule is planar. Two of the ;O bonds are e@uivalent and
relatively short Athis can be e*plained by theories of resonance.
 The canonical forms show double bond character in these two
bonds, causing them to be shorter than typical ;O bonds.C, and
the third ;O bond is elongated because the O is also attached to
a proton.

2.# REACTIONS

2.#.1 ACID$BASE PROPERTIES

;itric acid is normally considered to be a strong acid at ambient


temperatures. The pG 
a value is usually reported as less than M1.

 This means that the nitric acid in solution is fully dissociated


 

2+

e*cept in e*tremely acidic solutions. The pG a value rises to 1 at a


temperature of 2$0 %&.

;itric acid can act as a base with respect to an acid such as


sulfuric acid.

:;O# N 2:2'O4  ;O2N N :#ON N 2:'O4

 The nitronium ion, ;O2N, is the active reagent in aromatic nitration


reactions. 'ince nitric acid has both acidic and basic properties it
can undergo an autoprotolysis reaction, similar to the self
ioni!ation of water

2:;O#  ;O2N N ;O# N :2O

2.#.2 REACTIONS WITH METALS

;itric acid reacts with most metals but the details depend on the
concentration of the acid and the nature of the metal. 7ilute nitric
acid behaves as a typical acid in its reaction with most metals.
?agnesium, manganese  and !inc  liberate :2. Others give the
nitrogen o*ides. A<babio 200+C

;itric acid can o*idi!e nonactive metals such as copper  and


silver. Kith these nonactive or less electropositive metals the
products depend on temperature and the acid concentration. )or
e*ample, copper  reacts with dilute nitric acid at ambient
temperatures with a #E( stoichiometry  to produce nitric o*ide
 

2(

which may  react with atmospheric o*ygen to give nitrogen


dio*ide.

# &u N ( :;O #  # &u2N N 2 ;O N 4 :2O N 3 ;O#

Kith more concentrated nitric acid, nitrogen dio*ide is produced


directly in a reaction with 1E4 stoichiometries.

&u N 4 : N N 2 ;O#M  &u2N N 2 ;O2 N 2 :2O

=pon reaction with nitric acid, most metals give the corresponding
nitrates. 'ome metalloids  and metals give the o*ides, for
instance, 'n, <s, 'b, Ti are o*idi!ed into 'nO2, <s2O$, 'b2O$  and
 TiO2 respectively.

'ome precious metals, such as pure gold  and platinum group


metals do not react with nitric acid, though pure gold does react
with a@ua regia, a mi*ture of concentrated nitric acid and
hydrochloric acid. :owever, some less noble metals A<g, &u, ...C
present in some gold alloys relatively poor in gold such as colored
gold can be easily o*idi!ed and dissolved by nitric acid, leading to
color changes of the goldalloy surface. ;itric acid is used as a
cheap means in  5ewelry  shops to @uic"ly spot lowgold alloys
AQ 14 caratsC and to rapidly assess the gold purity.

Deing a powerful o*idi!ing agent, nitric acid reacts violently with


many nonmetallic compounds and the reactions may be
e*plosive. eaction ta"es place with all metals e*cept the noble
metals  series and certain alloys. <s a general rule, o*idi!ing
 

2>

reactions occur primarily with the concentrated acid, favoring the


formation of nitrogen dio*ide  A;O2C. A<babio 200+C :owever, the
powerful o*idi!ing properties of nitric acid are thermodynamic  in
nature, but sometimes its o*idation reactions are rather
"inetically nonfavored. The presence of small amounts of nitrous
acid A:;O2C greatly enhances the rate of reaction.

<lthough chromium  A&rC, iron  A)eC and aluminum  A<lC readily


dissolve in dilute nitric acid, the concentrated acid forms a metal
o*ide layer that protects the bul" of the metal from further
o*idation. The formation of this protective layer is called
passivation. Typical passivation concentrations range from 20
$0 by volume A<'T? <>3+0$ 2000C. ?etals which are
passivated by concentrated nitric acid are 6ron, &obalt, &hromium,
;ic"el, and <luminum.

2.#.3 REACTIONS WITH NON$METALS

Deing a powerful o*idi!ing acid, nitric acid reacts violently with


many organic materials and the reactions may be e*plosive. AGent
1>(#C

eaction with nonmetallic elements, with the e*ceptions of 


nitrogen, o*ygen, noble gases, silicon  and halogens, usually
o*idi!es them to their highest o*idation states as acids with the
 

#0

formation of nitrogen dio*ide  for concentrated acid and nitric


o*ide for dilute acid. A<babio 200+C

& N 4 :;O #  &O2 N 4 ;O2 N 2 :2O


O
# & N 4 :;O #  # &O2 N 4 ;O N 2 :2O

&oncentrated nitric acid o*idi!es 62, P 4 and '( into :6O#, : #PO4 and


:2'O4 respectively.

2.#.4 XANTHOPROTEIC TEST

;itric acid reacts with proteins to form yellow nitrated products.


 This reaction is "nown as the *anthoproteic reaction  AHregory
1>>>C. This test is carried out by adding concentrated nitric acid
to the substance being tested, and then heating the mi*ture. 6f 
proteins that contain amino acids with aromatic rings are present,
the mi*ture turns yellow. =pon adding a strong base such as
li@uid ammonia, the color turns orange. These color changes are
caused by nitrated aromatic rings in the protein.   Ranthoproteic
acid  is formed when the acid contacts epithelial cells  and is
indicative of inade@uate safety precautions when handling nitric
acid

2.% USES

2.%.1 NITRIC ACID IN A LABORATORY.


 The main use of nitric acid is for the production of fertili!ers. ;itric
acid is neutrali!ed with ammonia to give ammonium nitrate.
 

#1

<ccording to Hregory A1>>>, p.40(C this application consumes +$


(0 of the 23? tons produced annually. The other main
applications are for the production of e*plosives, nylon
precursors, and specialty organic compounds.

2.%.2 PRECURSOR TO ORGANIC NITROGEN COMPOUNDS

6n organic synthesis, industrial and otherwise, the nitro group is a


versatile functionality. ?ost derivatives of aniline are prepared via
nitration of aromatic compounds followed by reduction. ;itrations
entail combining nitric and sulfuric acids to generate the
nitronium ion, which electrophilically reacts with aromatic
compounds such as ben!ene. AHregory 1>>>C ?any e*plosives,
e.g. T;T, are prepared in this way.

 The precursor to nylon, adipic acid, is produced on a large scale


by o*idation of cyclohe*anone and cyclohe*anol with nitric acid.

1.%.3 ROCKET FUEL

;itric acid has been used in various forms as the o*idi!er in li@uid
fueled roc"ets. These forms include red fuming nitric acid, white
fuming nitric acid, mi*tures with sulfuric acid, and these forms
with :) inhibitor. 6);< Ainhibited red fuming nitric acidC was one
of # li@uid fuel components for the DO?<&  missile. AHregory
1>>>C

2.%.4 ANALYTICAL REAGENT


 

#2

6n elemental analysis dilute nitric acid A0.$ to $.0C is used as a


matri* compound for determining metal traces in solutions.
=ltrapure trace metal grade acid is re@uired for such
determination, because small amounts of metal ions could aJect
the result of the analysis. AGir" 1>(1C

6t is also typically used in the digestion process of turbid water


samples, sludge samples, solid samples as well as other types of 
uni@ue samples which re@uire elemental analysis via -ame atomic
absorption spectroscopy. Typically these digestions use a $0
solution of the purchased :;O# mi*ed with deioni!ed water.

6n electrochemistry, nitric acid is used as a chemical doping agent


for organic semiconductors, and in puri8cation processes for raw
carbon nanotubes.

2.%.# WOODWORKING

6n a low concentration Aappro*imately 10C, nitric acid is often


used to arti8cially age pine  and maple. The color produced is a
greygold very much li"e very old wa* or oil 8nished wood Awood
8nishingC.

2.%.% ETCHANT AND CLEANING AGENT

 The corrosive eJects of nitric acid are e*ploited for a number of 
specialty applications, such as pic"ling stainless steel. < solution
of nitric acid, water and alcohol, ;ital, is used for etching of 
metals to reveal the microstructure AHregory 1>>>C. &ommercially
 

##

available a@ueous blends of $#0 nitric acid and 1$40


phosphoric acid are commonly used for cleaning food and dairy
e@uipment primarily to remove precipitated calcium and
magnesium compounds Aeither deposited from the process
stream or resulting from the use of hard water during production
and cleaningC. The phosphoric acid content helps to passivate
ferrous alloys  against corrosion by the dilute nitric acid.A<non
1>+>C ;itric acid can be used as a spot test for al"aloids, giving a
variety of colors depending on the al"aloid.

2.& SAFETY 

;itric acid is a strong acid  and a powerful o*idi!ing agent. The


ma5or ha!ard posed by it is chemical burns as it carries out acid
hydrolysis  with proteins  AamideC and fats AesterC which
conse@uently decomposes living tissue  Ae.g. s"in  and -eshC.
&oncentrated nitric acid stains human s"in  yellow due to its
reaction with the "eratin. These yellow stains turn orange when
neutrali!ed. 'ystemic eJects are unli"ely, however, and the
substance is not considered a carcinogen or mutagen.

 The standard 8rst aid treatment for acid spills on the s"in is, as for
other corrosive agents, irrigation with large @uantities of water.
Kashing is continued for at least ten to 8fteen minutes to cool the
tissue surrounding the acid burn and to prevent secondary
damage. &ontaminated clothing is removed immediately and the
underlying s"in washed thoroughly. AOthmer et al 1>(1C
 

#4

Deing a strong o*idi!ing agent, reactions of nitric acid with


compounds such as cyanides, carbides, metallic powders can be
e*plosive  and those with many organic compounds, such as
turpentine, are violent and hypergolic Ai.e. selfignitingC. :ence, it
should be stored away from bases and organics.

2.' PINCH TECHNOLOGY IN MODERN PLANTS


One of the most successful and generally useful techni@ues is that
developed by Dodo 9innhoJ and other wor"ersE pinch technology .
 The term derives from the fact that in a plot of the system
temperatures versus the heat transferred, a pinch usually occurs
between the hot stream and cold stream curves. A'innot 200$C
Pinch technology is a relatively modern engineering tool
developed in the late 1>+0s and early 1>(0s. This new approach
to evaluating the energy re@uirements of a site @uic"ly identi8ed
ways of improving the overall energy use. The name Spinch
technology was applied because the techni@ue identi8ed the
point or points in the energy -ow where restrictions applied and
hence limited ones ability to reuse low grade energy.
  The ma5or diJerence between this new technology and the
previous engineering approaches was the formali!ed
methodology involving the rigorous application of thermodynamic
principles. Pinch technology was initially adopted by ma5or
chemical companies and petrochemical energy. Deet sugar was
@uite @uic" to adopt it because of the industrys energy pro8le
and it is now being adopted by the cane industry too. 6t has also
been shown that the pinch represents a distinct thermodynamic
 

#$

brea" in the system and that, for minimum energy re@uirements,


heat should not be transferred across the pinch, A9innhoJ et al
1>(#C
2.'.1 APPLICATIONS

Pinch technology is e@ually applicable to Hreen8eld pro5ect and


refurbishments. 6n either case, their ob5ectives are to achieveE

1. ?inimum energy consumption


2. Optimi!ation of utilities
#. ?inimum capital e*penditure to achieve these
?inimi!ing energy consumption implies minimi!ing cooling water
re@uirements too because all of the energy used ultimately has to
be re5ected again in some low grade form. A 'innot 200$C

 The technology strength are its overall approach to process


integration Arather than optimi!ing a single stationC and its blend
of thermodynamics with commercial re@uirements. 6t also ta"es
into account the operational re@uirements of the site and does
reduce -e*ibility or availability.

2.( PLANT LOCATION

Plant location refers to the choice of a region or the selection of a


particular site for settling up the business or a factory. :owever,
the choice is made only after considering alternative sites. 6t is a
strategic decision that cannot be changed once it is ta"en.
 

#3

 Therefore, careful care must be ta"en before a decision is made


on the location of the plant site Aay et al 1>(>C.

2.(.1 IDEAL PLANT LOCATION

<n ideal plant location is one where the cost of the production is
minimal, with a large mar"et availability, least ris" involved and
ma*imum gain obtainable. 6t is a place of ma*imum net
advantage or with lowest unit cost of production and distribution.
)or achieving this ob5ective, small and large scale entrepreneur
can ma"e use of local analysis.

2.(.2 LOCAL ANALYSIS

9ocal analysis is a dynamic process where the entrepreneur


analyses and compares the feasibility of diJerent sites with the
aim of selecting the best site for a given enterprise. 6t considers
the followingE

a. D)*+-/ !!5  it involves the study of the


population in the area in terms of total number of people in
the area, age composition, per capital income, educational
level and occupational structures etc.
b. T-6) -) !!5   it is an analysis of the geographic
area that provides continued clientele to the industry. 6t is
advisable to also see the feasibility of accessing the trade
area from alternative sites. Aay et al 1>(>C
c. C+*)778) !!5  it helps to 5udge the nature,
location, si!e and @uality of competition in a given trade
area.
 

#+

d. T-9 !!5 this is done to have a rough idea about the


number of potential customers passing by the proposed site
during the wor"ing hours of the industry. The trac analysis
aims at 5udging the alternative sites in terms of pedestrian
and vehicular trac passing by the site.
e. S7) )++*!5 alternative sites are evaluated in terms of 
establishments, costs and operational costs under this. &ost
of establishment of a plant is basically cost incurred for
permanent physical facilities but operation costs are incurred
for running the plant.

2.(.3 SELECTION CRITERIA

<ccording to ay A1>(>, p. +3C the important considerations for


selecting a suitable location are as followsE  

6. ;ature or climate conditions


66. <vailability and nearness to the sources of raw materials
666. Transport costsE this should be considered both for
obtaining raw material and also distribution or mar"eting
8nished products to the ultimate users.
IV. &lose pro*imity to the anticipated mar"etE   the industrys
warehouse should be located within the vicinity of densely
populated areas.
U. <vailability of infrastructural facilities such as developed
industrial shed or site, lin" roads, nearness to railway
stations, airports or seaports, availability of electricity,
 

#(

water, public utilities, civil amenities and means of 


communication are important.
U6. <vailability of s"illed and nons"illed labor and technically
@uali8ed and trained managers.
U66. Dan"ing and 8nancial institutions should be located
nearby.
U666. 'afety and security should be given due consideration
6R. Hovernment in-uencesE ta* relief, subsidies, liberation
and other positive policies of the government to support
the start oJ of any industry should be duly considered
before any industry is set up. <lso, negative government
in-uences li"e restrictions for setting up industries in an
area for reason of pollution control and decentrali!ation of 
industries should be considered.
R. =tility costs and availability.

2.(.4 SELECTION OF PLANT LOCATION FOR THE NITRIC


ACID PLANT

 There were three plant locations proposed. /ach was evaluated


and the 8nal decision based on ma*imum net advantage was
made.

2.(.4.1 LOCATION ONE5 AGBARA INDUSTRIAL ESTATE


:OGUN STATE;

A687)!

1. elatively cheap available land and labor cost.


2. elatively close to mar"et A9agos ;ylon and plastic mar"etC.
#. elatively close to sea A9agos <papaC for import of raw
material and e*port of product if need be.
 

#>

4. <vailability of infrastructural facilities such as lin" roads,


public utilities etc.
$. <vailability of 8nancial institution.
3. elatively secure.
+. <vailability of social amenities and means of communication.
(. D!687)!
1. ;o local source of raw material nearby meaning all raw
materials have to be transported to the plant location.
2. The ma5or roads that will be used for transportation Ai.e form
<papa to <gbaraC are bad and one is prone to e*perience
hold up on it.
#. Transport cost will be very high for both bringing in of raw
material and mar"eting 8nished product as the target mar"et
is 9agos and things are "nown to be very e*pensive there.
4. The ;ylon and plastic mar"et in 9agos is not large enough to
e*haust all nitric acid produced by the plant.
$. <dditional cost of providing water and electricity for the
plant.

2.(.4.2 LOCATION TWO5 ABA :ABIA STATE;

A687)!

1. elatively cheap available land and labor cost.


2. <vailability of mar"et Aplastic and ;ylon mar"etC
#. <vailability of 8nancial institution.
4. elatively secure.
$. <vailability of social amenities and means of communication.

D!687)!
 

40

1. ;ot close to source of raw material


2. <dditional cost of providing water and electricity for the
plant.
#. ?ar"et available not enough to e*haust all nitric acid
produced in the plant.
4. 9ac" of infrastructural facilities such as sea port, airport and
railway stations nearby.

2.(.4.3 LOCATION THREE5 ELEME, PORT$HARCOURT


:RIVERS STATE;

A687)!

1. &lose to source of raw materialE ;ational )ertili!er &ompany


of ;igeria A;<)&O;C, an ammonia and fertili!er plant at
Onne, Port:arcourt, ivers 'tate bought over by ;otore
started operation in Van 200>. Their production of ammonia
per day of ammonia was 1,000?T as at 200> of anhydrous
ammonia Amore than enough raw material for our nitric acid
plantC. /leme Petrochemical located in /leme, Portharcourt,
ivers 'tate is also billed to come up with an ammonia plant
in 2014 which will ma"e available to the ;igeria mar"et
2#00?T.
2. <vailability of mar"et in Port:arcourt, closeness to sea for
e*port of product if necessary.
#. <vailability of public utilities such as water, sea port, airport,
etc.
4. <vailability of both s"illed and uns"illed labor.
$. <vailability of ban"ing and 8nancial institutions.
3. <vailability of social amenities and means of communication.
+. elatively secure.
 

41

D!687)!

2. :igh cost of land


#. ;o regular power supply

2.(.# PLANT LAYOUT

:aving selected a suitable site for the chemical plant, it is


possible and necessary to ma"e a preliminary decision regarding
the layout of the plant e@uipment. Aay et al 1>(>C <lthough the
e@uipment has not been designed in detail, preliminary estimates
of the physical si!e of each item should be available in the
e@uipment list. <ny si!ing diJerences between the initial and 8nal
estimates should not be too e*cessive, and appropriate areas
should be allowed around the plant items when determining the
layout.

< preliminary determination of the plant layout enables


consideration of pipe runs and pressure drops, access for
maintenance and repair and in the event of accidents and spills,
and location of the control room and administrative oces. The
preliminary plant layout can also help to identify undesirable and
unforeseen problems with the preferred site, and may necessitate
a revision of the site selection. ADaasel 1>(>C The proposed plant
layout must be considered early in the design wor", and in
sucient detail, to ensure economical construction and ecient
operation of the completed plant. The plant layout adopted also
aJects the safe operation of the plant, and acceptance of the
 

42

plant Aand possibly any subse@uent modi8cations or e*tensionsC


by the community.

 There are two schemes that can be adopted for determination of 
the plant layout. ADuc"hurst W :ar"er 1>+#C )irst, the I-ow
through layout Aor I-owline patternC where plant items are
arranged Ase@uentiallyC in the order in which they appear on the
process -ow sheet. This type of arrangement usually minimi!es
pipe runs and pressure drops Aand is often adopted for small
plantsC. 'econd, the e@uipment is located on site in groupings of 
similar plant items, e.g. distillation columns, separation stages,
reactors and heat e*changer preheaters, etc. The grouped
pattern is often used for larger plants and has the advantages of 
easier operation and maintenance, lower labor costs, minimi!ing
transfer lines and hence reducing the energy re@uired to transfer
materials. These two schemes represent the e*treme situations
and in practice some compromise arrangement is usually
employed. The plant layout adopted depends upon whether a new
AIgrass rootsC plant is being designed or an
e*tensionmodi8cation to an e*isting plant. 'pace restrictions are
the most common constraintsF however, space limitations are
usually imposed even with new sites. Other factors to be
considered areE

 AaC 'iting of the control room, oces, etc., away from areas of 
high accident ris", and upstream of the prevailing winds.
 

4#

AbC 9ocation of reactors, boilers, etc., away from chemical storage


tan"s.

AcC 'torage tan"s to be located for easy access, and a decision


made as to whether all tan"s Afor raw materials and productC
should be located together or dispersed around the site.

AdC 9abor re@uired for plant operation.

AeC /levation of e@uipment.

AfC e@uirements of speci8c plant items, e.g. pumps.

AgC 'upply of utilities, e.g. electricity, water, steam, etc.

AhC ?inimi!ing plant piping systems.

AiC 'uitable access to e@uipment re@uiring regular maintenance or


repair.

A5C Plant layout to facilitate easy cleanup operations and


dispersion of chemicals in the event of a spillage.

A"C <ccess to the plant in the event of an accident.

A1C 'iting of e@uipment re@uiring cooling water close to rivers,


estuaries, etc.

AmC 9ocation of plant waste and water drainage systems Aseparate


or combinedXC and treatment tan"s.

AnC <dopting a plant layout that will act to contain any 8res or
e*plosions.
 

44

AoC 'pacing between items of e@uipment Ainsurance companies


speciali!ing in the insurance of chemical plants have speci8c
recommendations for the distances re@uired between particular
items of e@uipmentC.

 The layout of plant e@uipment should aim to minimi!eE

AiC damage to persons and property due to 8re or e*plosionF

AiiC ?aintenance costsF

AiiiC ;umber of plant personnelF

AivC Operating costsF construction costsF

AvC &ost of plant e*pansion or modi8cations.

'ome of these aims are con-icting, e.g. AiC and AivC, and
compromises are usually re@uired when considering the plant
layout to ensure that safety and economic operation are both
preserved. The 8nal plant layout will depend upon the measures
for energy conservation within the plant and any subse@uent
modi8cations, and the associated piping arrangements.

 The process units and ancillary buildings are laid out in such a
way to give the most economical -ow of materials and personnel
around the site. :a!ardous processes are located a safe distance
from other buildings. &onsideration for future e*pansion is also
put in place. The ancillary buildings and service re@uired on the
site includeE

 <dministrative bloc"
 

4$

 9aboratory
 'torage for both raw materials and products
 ?aintenance wor"shop
 =tilities Agenerator, steam boiler, transformer stationC
 'tore for maintenance and operation supplies
 Other amenities li"e car par", restaurant and clinic.

E*)-,)214
F0-) S770+2 W7)-

T2< F-* P327 A-)

S7+-)!
W+-<!/+.

R+6!

C27))2
M)6013
C)27)-
W!7) C- P1< 
U703070)!
I2102)-7+-
A=607+-0=*
O91)!

R+6!

)ig 1.1 /*pected plant layout.

2.(.% PROCESS ROUTES FOR THE PRODUCTION


OF NITRIC ACID

CHILE SALTPETRE>NITRATE PROCESS


 

43

&hile saltpetre is material which contains sodium nitrate ;a;O #


with percentage around #$30, and remaining percentage
compounds with G;O# and ;a&l. This raw material &hile saltpetre
is concentrated by crystalli!ation in pretreatment of ore to attain
>$ ;a;O# and remaining G;O# as feed raw material. AGent 1>(#C

'ulphuric acid with ># is mi*ed with the re8ned &hile saltpetre
as per the ratio re@uired as per stoichiometry and sent into a
retort which is made with cast iron and the mi*ture is heated to
200o& with help of furnace -ue gasses and coal 8re. Thus at this
temperature, the following reaction is carried forward to produce
:;O#, nitric acid vapors.

  ;a;O# N :2'O4  ;a:'O4 N :;O#

<ll hot vapors of nitric acid are sent to cool down in water
circulated cooled silica pipes, condensed :;O# are collected in
receiver which has material resistance to nitric acid. =ncondensed
gas which escapes from the collector is scrubbed with cooled
water in pac"ed bed tower to collect nitric acid in dilute format.
9i@uid sodium bisulphate is collected from the bottom outlet of 
the retort.

A687)5  it was one of the 8rst methods used in the


manufacture of nitric acid.

D!687)5 source of raw material can be e*hausted.


 

4+

F 1.25 ?anufacture of nitric acid from &hile 'altpetre.

BIRKELAND$EYDE PROCESS>ARC PROCESS

 This process is based upon the o*idation of atmospheric nitrogen


by atmospheric o*ygen to nitric o*ide at very high temperature.
<n electric arc is used to provide the high temperatures, and
yields of up to 4 nitric o*ide were obtained. A Ohrue 1>>>C

;2 N O2 2;O

 The nitric o*ide was cooled and o*idi!ed by the remaining


atmospheric o*ygen to nitrogen dio*ide

  2 ;O N O2 2;O2

 This nitrogen dio*ide is then dissolved in water to give dilute nitric


acid.
 

4(

# ;O2 N :2O  2:;O# N ;O

A687)E unlimited source of raw material AairC

D!687)E The process is very energy intensive and is only


feasible when electricity is available and cheap.

WINSCONSIN PROCESS>NITROGEN FIXATION PROCESS

<tmospheric o*ygen and nitrogen are combined in a high


temperature regenerative furnace operating at about 2000o&.
;itric o*ide is formed with a yield of nearly 2.

A687)E it does not use electricity to provide the high


temperature and therefore does not have the disadvantage of the
Dir"eland/yed process.

D!687)E cannot compete favorably with the Ostwald


process.

<nother method of production of nitric acid via nitrogen 8*ation is


the nuclear nitrogen 8*ation route. This method directly combines
o*ygen and nitrogen. Yields of nitrogen o*ide of $1$ have been
reported by e*posing air at 1$0 and 400 o) to radiation from
=ranium 2#$.

A687)5  gives a greater yield of nitrogen o*ide than the


Kinsconsin process

D!687)5 with this method comes all the disadvantages of 


nuclear reaction Aproblem of managing the radiation which is
harmful to living thingsC
 

4>

OSTWALD PROCESS

6n this process, anhydrous ammonia is o*idi!ed to nitric o*ide, in


the presence of platinum or rhodium gauge catalyst at high
temperature of about $00G and a pressure of >bar. Aay et al
1>(>C

4 ;:# AgC N $ O2 AgC  4 ;O AgC  N 3 :2O AgC AZ:[ >0$.2GVC

;itric acid is then reacted with o*ygen in air to form nitrogen


dio*ide.

2 ;O AgC  N O2 AgC  2;O2 AgC AZ:[ 114GVmolC

 This is subse@uently absorbed in water to form nitric acid and


nitric o*ide

# ;O2 AgC N :2O AlC  2 :;O# Aa@C N ;O AgC AZ:[ 11+GVmolC

 The nitric o*ide is cycled bac" for reo*idation. <lternately, if the


last step is carried out in airE

4 ;O2 AgC N O2 AgC N 2:2O AlC  4:;O# Aa@C

 The a@ueous :;O#  obtained can be concentrated by distillation


up to about 3( by mass.

 There are 2 basic types of systems used to produce wea" nitric


acidE

Doth processes follow the basic Ostwald process for the catalytic
o*idation of ammonia. 6n summary, this involves an o*idation
stage whereby ammonia is reacted with air in a catalytic
 

$0

converter at temperatures in the range of ($0>$0%&. eaction


gases pass through a series of energy recovery stages before
entering an absorption column. The bottoms from the column are
bleached of dissolved nitrogen pero*ide using air, and the
resulting solution is the wea" nitric acid product Aoudier et al
1>+>C.

 The ma5or diJerence between the two processes lies in the initial
conversion stage. The dualpressure process employs a
conversion stage operating in the range l00#$0"Pa, and a reactor
temperature of about (3$%&. The singlepressure process however
operates the converter at (001100 "Pa, with a reactor
temperature closer to >40%&. A :arvin et al 1>+>C

1. S)$!7) -)!!=-) -+)!! E in this case, the plant is


operated at a single pressure throughout.
 

$1

)ig 1.#. Process -ow diagram for singlestage pressure process.


A687)5
• 9ess e*pensive as less e@uipments are used.
•  The singlepressure process uses a higher ammonia
conversion pressure. This higher pressure provides
advantages in terms of e@uipment design, e.g. smaller
converter dimensions and a single heate*changertrain
layout.A 9eray et al 1>+>C
•  The higher temperature and the favorable pressure both
increase the energy recovery from the process.
• 9imited space availability may favor the singlepressure
process
D!687)5 
 

$2

• 9ess ecient as the overall process is favored by varying


pressure.
• /*perimental wor" indicates that the rate loss of catalyst
Awithout a catalyst recovery systemC is appro*imately three
times more rapid at >+#%& than at (33%&. This means that
more catalyst is lost in the singlestage pressure process
A :arvin et al 1>+>C.
• <bsorber eciency is reduced prompting the need for larger
absorber thereby increasing cost.
2. D=$!7) -)!!=-) -+)!!E here, the plant is operated
at diJerent pressures and diJerent stages.
A687)!E
•  The 8rst reaction Acatalytic conversion of anhydrous
ammonia to nitric o*ideC is favored by lower pressure while
the remaining reactions are favored by higher pressures.
 This variation in pressure is achieved in dualstage pressure
process. A:arvin et al 1>+>C
•   &apacities of 11#01#30 tonnes per day favor the dual
pressure process, because of the possibility of absorption up
to 1$$0 GPa.
• 9ess catalyst is lost because of lower operating temperature
 

$#

)ig 1.4. Process -ow diagram for dualstage pressure process.

 The process selected for this design of nitric acid is singlestage


pressure Ostwald process because of its above mentioned
advantages.
 

$4

)ig1.$E 'elected Process -ow diagram for ;itric acid plant.

CHAPTER THREE
 

$$

MATERIAL BALANCE

?aterial balance is one of the most important components of a


process design. Overall raw material of the entire process
determines the @ualities of raw materials re@uired and the
products produced in the process.

Dalance over individual process units determines the process


stream -ows and their compositions and also the si!es of the
various process e@uipment used in the process.

?aterial balance on the plant used in the production of 400000


tonnes of ;itric acid per year.

kg kg
?ass -ow rate [ 400000 * 1000  year  [ $0000 hr

3.1 CONSERVATION OF MASS

)or a steady state process, the accumulation term will be !eroF


but if a chemical reaction ta"es place, particular chemical specie
may be formed or consumed in the process. Khen there is
chemical reaction, the material balance e@uation is given as,

6nput N Heneration [ Output N &onsumption

6f there is no chemical reaction, the steady state balance reduces


toF

6nput [ Output
 

$3

< balance e@uation can be written for any identi8able specie


present, elements or compoundF and for the total material.

3.2 METHODS OF MATERIAL BALANCE

 There are two basic methods of material balance and they areF

AaC A)?- M)7/+6

 The algebraic method of material balancing is one of the simplest


and most common methods applied in balancing the materials
that -ow through a system. 6t involves the systematic and
se@uential techni@ue in indentifying some variable sets which are
related by some sets of linear or nonlinear e@uations whose
solution depends on the resulting degree of freedom for the
system. This degree of freedom provides us with the limit of 
freedom for which we can set values for some of the variable
which is referred to as the design variables. < choice of values for
the design variables result in a corresponding value for the
remaining variables. The solutions to the e@uation set are
obtained by the various method of solution for simultaneous
e@uations, most appreciably the methods of substitution and
elimination. The algebraic method is most ecient for simple
system but it may be inappropriate for comple* systems involving
large number of units. The split fraction and method is
recommended for such systems.

:?;. S7 F-7+ M)7/+6


 

$+

 This method is based on the theory of recycle processes


published by ?agier A1>34C. The method is based on the
reali!ation that the basic function of most chemical processing
units A=nit OperationC is to divide the inlet -ow of a component
between two or more outlet streams. This method is ideal in
carrying out material balancing of comple* of multiunit plants.

3.3 MATERIALS BALANCE ASSUMPTIONS

 The following assumptions were made during the material


balance calculationsE

1. The system is operating at steady state i.e. there is no


accumulation of any sort in the system.
2. There is negligible amount of inert in the process air.
#. easonably high conversion in the reactors.
4. /Ject of side reactions is minimal.
3.4 SUMMARY OF MATERIAL BALANCE
CALCULATIONS

)rom the steady state material balance e@uation, the -ow rates of 
each stream are calculated as follows.

3.# MATERIAL BALANCE FOR EACH UNIT

B!!5 1/-

THE COMPRESSOR

1a 1a

 'tream 1 'tream 2
 

$(

  'tream #

&omponents 'tream 1A "ghrC &omposition 'tream


1aA "ghrC
O2 4>+20. O2 4>+20.
;2 1(+0(0 ;2 1(+0(0
 Total 2#3+$0 Total 2#3+$0
 

THE MIXER

'tream 2 'tream $

'tream 4

 
 

$>

&omponents 'tream 2AGghrC 'tream 4 'tream $AGghrC


AGghrC

O2 42+30  42+30
;2 130(30  130(3
;:#    1#$00 1#$00

:2O  3$ 3$

 Total 20#320 1#$3$ 21+1($

 TOT<9 21+1($ 21+1($

THE COVERTER

'tream $ 'tream +

'tream 3

&omposition 'tream $ 'tream 3 'tream +


 

30

O2 42+30  11330
;2 130(30  130(30
;:# 1#$00 2+0 
:2O 3$ 21030 
;O   2##20
:;O#     
;O2     
 Total 21+1($ 21##0 1>$(40
 TOT<9 21+1($ 21+1+0

OXIDISATION VESSEL

'tream + 'tream (

&omponent 'tream + 'tream (


AGghrC AGghrC
O2 11330 
;2 130(30 130(30
;:#    
:2O  
;O 2##20 1430
:;O#    
;O2    ##$#0
 Total 1>$(40 1>$($0
 

31

ABSORBER  'tream 3 N ?a"e up water

'tream >

'tream (

&omponent 'tream 3 N 'tream ( 'tream >


ma"eup AGghrC AGghrC
water
AGghrC
O2     
;2    130(30 130(30
;:#   2+0  2+0
:2O 2(120  2#(#0
;O  1430 (300
:;O#    #0000
;O2    ##$#0 3+2
 Total 2(#>0 1>$($0 2242#2
 

32

 TOT<9 224240 2242#2

STRIPPER 'tream 10

'tream >

'tream # 'tream 11

&omponent 'tream > 'tream # 'tream 10 'tream 11


AGghrC AGghrC AGghrC AGghrC
O2    3>30 40#0 #0000
;2 130(30 231+0 130(30 
;:#   2+0   
:2O 2#(#0  4230 20000
;O (300  $(0 
:;O# #0000   
;O2 3+2  +230 
 Total 2242#2 ##1#0 1+3>>0 $0000
 TOT<9 2$+#32 223>>0
 
 

3#

COMBUSTION CHAMBER

  'tream 1#

  'tream 10

'tream 12

&omponent 'tream 10 'tream 12 'tream 1#


AGghrC AGghrC
O2 40#0 #+#+0 2440
;2 130(30 140$(0 #01440
;:#     
:2     ##0
:2O 4230  23+10
;O $(0  410
:;O#     
;O2 +230  +$20
&:4     (30
&2:3     $0
&O2     244(0
 Total 1+3>>0 1++>$0 #34240
 TOT<9 #$4>40 #34240
 

34

PURIFICATION REACTOR

'tream 1# 'tream 14

&omponent 'tream 1# 'tream 14


AGghrC AGghrC
O2 2440 23+0
;2 #01440 #0#+>0
;:#    
:2   ##0 1+0
:2O 23+10 #02#0
;O 410 20
:;O#    
;O2 +$20 #(0
&:4 (30 
&2:3 $0 
&O2 244(0 2+000
 Total #34240 #34230

 Table #.1E 'ummary of ?aterial balance on each stream.

'T/< &O?PO;/;T )9OK <T/ AGghrC TOT<


?' 9
 

3$

:;O &: &2


O2 ;2 ;:# :2O ;O ;O2 &O2
# 4 :3
4>+2 1(+0 2#3+
1        
0 (0 $0
4>+2 1(+0 2#3+
1a        
0 (0 $0
442+ 130( 20#3
2        
30 30 20
231+ ##1#
# 3>30        
0 0
1#$ 1#$3
4   3$      
00 $
42+3 130( 1#$ 21+1
$ 3$  
0 30 00 (0
210 21##
3   2+0      
30 0
1133 130( 2## 1>$(
+       
0 30 20 40
130( 143 ##$ 1>$(
(       
30 0 #0 $0
130( 2#( (30 #00 2242
>  2+0 3+0   
30 #0 0 00 #2
130( 423 +23 1+3>
10 40#0 $(0    
30 0 0 >0
#000 200 $000
11        
0 00 0
#+#+ 140$ 1++>
12        
0 (0 $0
#014 23+ +$2 (3 244 #342
1# 2440  410  $0
40 10 0 0 (0 40
#0#+ #02 2+0 #342
14 23+0  20  #(0  
>0 #0 00 30

 Table #.2E Process matri* of the ;itric acid production process

/\=6P?/;T <''O&6<T/
 

33

;=?D/ ;<?/ 'T/<?'


1 &O?P/''O 1, 1a
2 'P96TT/ 1a, 2, #
# ?6R/ 2,4, $
4 &O;U/T/ $, 3, +
$ OR676'<T6O; =;6T +, (
3 <D'OD/ 3, (, >
+ 'T6PP/ #, >, 10, 11
( &O?D='T6O; 10, 12, 1#
&:<?D/
> P=6)6&<T6O; 1#, 14
/<&TO

CHAPTER FOUR
ENERGY BALANCE

 The /nergy balance gives the account of all the energy


re@uirement of the process which is based on the principle of 
conservation of energy. The principle states that energy can
either be create nor destroyed but can be transformed from one
form to another. <lso energy can be transferred from one body to
another.

6f a plant uses more energy than its competitor, its product could
be priced out of the mar"et. <ccountability of the energy
utili!ation of a process plant is necessary in every design pro5ect.

 The conservation of energy however diJers from the mass in that


energy can be generated Aor consumedC in a chemical process.
 

3+

?aterial can change formF new molecular specie can be formed in


a process unit and must be e@ual to the one out at steady state.
 The same is not true for energy. The total enthalpy of the outlet
stream will not be e@ual to that of the inlet stream if energy is
generated or consumed in the processes, such as that due to heat
of reaction.

/nergy can e*ist in various formsE head, mechanical, electrical


energy, and it is the total energy that is conserved. 6n plant
operation, an energy balance on the plant will show the patterns
of energy usage and suggest area for conservation and saving.

4.1 CONSERVATION OF ENERGY 

<s for materials balance, a general e@uation can be written for


energy balanceF

/nergy out  /nergy in N Heneration  &onsumption [


<ccumulation

 This is a statement of the 8rst law of thermodynamics. <n energy


balance can be written for any process step. &hemical reactions
will evolve energy Ae*othermicC or consume energy
AendothermicC. )or steady state processes, the accumulation of 
both mass and energy will be !ero A0C.
 

3(

/nergy e*ists in many formsF the basic forms are listed belowE

P+7)7 E)-5 This is due to position or height due to motion

I7)- E)-5 This is the energy associated with molecules


and is dependent on temperature.

W+-<5  This is achieved when a force gets through a distance.


Kor" done on a system is positive while wor" done by a system is
negative

K)7 E)-5 This is the energy due to motion.

  K \

B1
)or unit mass of material
B2
2 2
U 1 U 
U 1 + P1 V 1 +  + Z 1 g +Q =U 2+ P2 V 2 + 2 + Z 2 g + W 
g g

Khere, \ [ :eat transferred across the system boundary

K [ Kor" done by the system

  P1P2 [ Pressure in Pressure Out

  U1U2 [ Uolume in, Uolume out


 

3>

  =1=2 [ Uelocity in, Uelocity out

B1B2 [ :eight in, :eight out

  g [ <cceleration due to gravity A>.(1ms2C

(  )  
2

6n chemical processes the "inetic energy factor g and the

Potential energy factor A!gC are small and negligible and the
relation between = and PU is correlated in terms of enthalpy A:C

: [ = N PU

:2  :1 [ \  w

<lso, the wor" term can be negligible in many chemical


engineering systems. :ence,

:2  :1 [ \

4.2 ENERGY BALANCE ASSUMPTIONS

1. The process is at steady state

2. ;o heat is lost from the vessel and from the pipe i.e. there is
proper lagging.

#. /Ject of pressure on enthalpy is ignored .

4. Potential and "inetic energy changes are negligible.


 

+0

4.3 SUMMARY OF ENERGY BALANCE

THE COMPRESSOR

  Tin[ 20%& Tout[1$$%&

TABLE 4.15 HEAT BALANCE AROUND COMPRESSOR .

&omponent nin AGghrC :in AGVGgC nout AGHhrC :out AGVGgC


;2 1(+0#0 0 1(+0#0 140.4
O2 4>+20 (+.$3 4>+20 (+.$3

POP/T6/' \=<;T6TYU<9=/
6nlet TemperatureA %& C 20
Outlet TemperatureA %& C 1$$
:eat dutyA GVhr C 232$>012
Power and <ctual 'haft wor",   #>>$1$.4> and
repectively.AGVhr and GVC 4+$31#.3(

TABLE 4.2 HEAT BALANCE ABOUT THE AIR HEATER

F+- - +*+)7 7/7 !!)! 7/-+=/ 7/) - /)7)-

&omponent nin AGghrC :in AGVGgC nout AGHhrC :out AGVGgC


;2 1(+0#0 0 1(+0#0 (0.+>
O2 4>+20 1$2.4> 4>+20 1$2.4>
6nlet Temperature Ao&C 1$$
Outlet Temperature Ao&C 200
:eat 7utyA GVhr C 1$10+>43.+$

F+- 7-+=! !)! -))6 ?< 7+ 7/) - /)7)-


 

+1

POP/T6/' \=<;T6TYU<9=/
6nlet TemperatureA %& C #$0
Outlet TemperatureA %& C 200

&omponent nin AGghrC :in AGVGgC nout AGHhrC :out AGVGgC


  ;2 130(30 131.10 130(0 131.10
  ;O 1430 0 1430 1$$.11
  ;O2 ##$#0 1>3.$ ##$0 1>3.$
:eat 7utyA GVhr C 223430.3

TABLE 4.3 HEAT BALANCE AROUND THE CONVETER

&omponent nin AGghrC :in AGVGgC nout AGHhrC :out AGVGgC


;:# 1#$00 0 2+0 1>02.>>
O2 42+30 312.$( 11330 312.$(
;O2     2##20 310.#(
;2 130(30 3>#.3# 130(30 3>#.3#
:2O 3$ 1#0>.44 21030 1#0>.44
:eat 7utyA GVhr C 20$+>2+#.(# GVhr

TABLE 4.4 HEAT BALANCE AROUND THE WASTE HEAT


BOILER :U7 (;

&omponent nin AGghrC :in AGVGgC nout AGHhrC :out AGVGgC


  O2 11330 33>.( 11330 33>.(
  ;2 130(30 +1>.2$ 130(30 +1>.2$
  ;O 2##20 0 2##20 3($.0>
POP/T6/' \=<;T6TYU<9=/
6nlet TemperatureA %& C (>0
Outlet TemperatureA %& C 2$0
:eat 7utyA GVhr C 1$>+32$2
Outlet Temperature of 'team   410
A%& C
 

+2

TABLE 4.# HEAT BALANCE AROUND THE OXIDI@ING VESSEL

&omponent nin AGghrC :in AGVGgC nout AGHhrC :out AGVGgC


 O2 11330 100.2+  
;2 130(30 10+.(0 130(30 10+.(0
;O 2##20 0 1430 10#.>3
;O2     ##$#0 1#1.00

POP/T6/' \=<;T6TYU<9=/
6nlet TemperatureA %& C 2$0
Outlet TemperatureA %& C #$0
:eat 7utyA GVhr C 1240(>1.$4

TABLE 4.% HEAT BALANCE AROUND THE STACK GAS


HEATER

&omponent nin AGghrC :in AGVGgC nout AGHhrC :out AGVGgC


  ;2 130(30 $2.>0> 130(30 $2.>0>
  ;O 1430 0 1430 +1>.2$
  ;O2 ##$#0 3$.$0 ##$#0 3$.$0
POP/T6/' \=<;T6TYU<9=/

6nlet TemperatureA %& C 1$0


Outlet TemperatureA %& C $0
:eat 7utyA GVhr C 14>+(1.4
:eat 7uty of 'teamA GVhr C +4#22.+3
 Temperature of 'team A%& C 11(.4(

TABLE 4.& HEAT BALANCE AROUND THE ABSORPTION


COLUMN
 

+#

&omponent nin AGghrC :in AGVGgC nout AGHhrC :out AGVGgC


;:# 2+0 0 2+0 $+3.4(
:2O 2(120 11+$>+.(4 2#(#0 >>3$+.0
;2 130(30 13+313.12 130(30 13+313.12
;O 1430 14#+.33 (300 ($(3.24
:;O#     #0000 $1300.0
;O2 ##$#0 4#>24.#> 3+0 ((0.#2

POP/T6/' \=<;T6TYU<9=/
6nlet TemperatureA %& C $0
Outlet TemperatureA %& C $4
:eat 7utyA GVhr C $#2(0.0#
 

+4

HEAT BALANCE AROUND THE AMMONIA VAPORI@ER,


SUPERHEATER AND STRIPPER.

  AMMONIA VAPORI@ER

:eat 7uty [ 14>+( GVhr

Outlet Temperature [ 2(.20 %&

  THE AMMONIA SUPPERHEATER

:eat 7uty [ 1$>32$2 GVhr

Outlet Temperature [ 23.3$ %&

  THE STRIPPER

:eat 7uty [ 2$(+#200 GVhr

6nlet Temperature [ 2$0 %&

 Outlet Temperature [ 120%&


 

+$

CHAPTER FIVE
CHEMICAL ENGINEERING DESIGN

 The e@uipment used in chemical process industries can be divided


into two classesE proprietary e@uipment such as pumps,
centrifuge, etc which are designed and manufactured by
specialist 8rmsF nonproprietary e@uipment which includes the
reactor, heat e*changer, evaporators, still, condensers and
bleaching vessels.

 The proprietary e@uipment will only be selected and speci8ed


while the nonproprietary e@uipment will be designed as special,
oneoJ, items for the particular processes and purposes they are
e*pected to serve.

 The chemical /ngineers part in the design of Snonproprietary


e@uipment is usually limited to Sselecting and Ssi!ing the
e@uipment. 'ame will be done in this design wor".

#.1 PROCESS UNITS OF NITRIC ACID PRODUCTION


PLANT

 The nitric acid process plant comprisesE

1. I+$ E/) U7

 This unit consists of series of pac"ed beds containing various


organic polymer resins for the removal of unwanted divalent and
monovalent ions. =sed for the generation of deioni!ed water.
 

+3

2. D)$+)6 7)- C++)-

&onsist of 8nned fantype cooler for cooling the circulating de


ioni!ed water.

3. A- Co*-)!!+-

:ere air is compressed in two stages. The 8rststage compression


is a lowpressure compression from atmospheric pressure up to
#10 "Pa. <n a*ial compressor is used which ta"es its shaft drive
from a gas turbine. The second compression utili!es a centrifugal
type compressor. The centrifugal compressor is more ecient for
the air -owrate A#3 000 "ghC and outlet pressure A10>0 "PaC. The
centrifugal compressor ta"es its shaft drive from the e*pansion of 
tail gas. 6ntermediate to the two compression stages is an
intercooler which allows the air temperature to be lowered from
1(0%& to 4$%&, with a pressure loss of 10 "Pa. The temperature
drop enables a more ecient second compression stage.

4.  A**+ V+-)-

 This unit consists of a shell and tubetype heat e*changer with


two passes per shell on the tube side. Operating pressure is 1240
"Pa. The e*changer is made from mild steel.

#. A**+ S=)-$/)7)-
 

++

6t consists of a shell and tubetype heat e*changer of similar


mechanical construction to the ammonia vapori!er. 6t is
constructed from mild steel.

3.  R)7+-

 The reactor is a pressure vessel operating in the range 10$0 "Pa


to 1100 "Pa. The bottom section of the reactor is 5ac"eted. <ir is
preheated in this 5ac"et prior to mi*ing with ammonia. The bottom
section of the reactor also contains a shell and tubetype heat
e*changer. This e*changer provides the 8nal stage of tailgas
preheating. Tail gas enters at 2#$%& and the reaction gases leave
the e*changer section of the reactor at 34$%&.

+. S7)* S=)-$/)7)-

 This unit superheats saturated steam from 2$0%& Aand 4000"PaC


to #(0%&. The product steam is of medium pressure and suitable
@uality for Iinhouse application and also for e*port. The super
heater cools the reaction gases from the reactor e*it temperature
of 34$%& to $>$%&.

8. W!7)$/)7 B+)-

< shell and tubetype e*changer re@uired to heat pressuri!ed


A4000 "PaC hot water from 11+%& to a saturated vapour at 2$0%&.
 The wasteheat boiler cools reaction gases from $>$%& to 2(0%&.

9. T$! P-)$/)7)-
 

+(

<lso comprises of shell and tubetype e*changer. 6t ta"es reaction


gases leaving the platinum 8lter at about #1$%& and 1020 "Pa,
and subse@uently reduces their temperature to 1($%&. The
cooling medium is tail gas. 6t enters at about $0%& and leaves the
tailgas preheater at 2#$%&.

10. C++)->C+6)!)-

 This unit condenses wea" nitric acid from the gaseous mi*ture
and cools the remaining gases from an inlet temperature of 1($%&
to 30%&. The shell and tubetype heat e*changer uses deioni!ed
water as its cooling medium.

11. O67+ U7

 The o*idation unit is an empty pressure vessel that ta"es input


reaction gases and blends in additional air from the bleaching
column. The e*tra o*ygen provided enables further o*idation to
occur and raises the gas mi*ture temperature to 140%&. <t the
top of the o*idation unit is a mist eliminator to prevent carryover
of acid vapor by entrainment. <t the bottom of the vessel is the
wea"acid drain.

12. S)+6- C++)-

 The secondary cooler ta"es the e*it gases from the o*idation unit
at 140%& and cools them down to 3$%&, a suitable temperature for
entry into the absorption column. The cooling medium is
 

+>

circulating warm water from the warmwater loop. The inlet


temperature is $0%& and the e*it temperature is about (0%&.

13. A?!+-?)-

 The absorber is usually a sieve traytype column. 6t has an


operating pressure around >>0 "Pa. < bursting disc is used for
pressure relief. /ach tray is provided with cooling coils to allow the
cooling of the absorption li@uor. There are two independent
cooling circuits, each uses deioni!ed water. The top section has
an inlet temperature of +%& and an outlet temperature of 20%&.
 The bottom section cooling loop has an inlet temperature of 20%&
and an e*it of 40%&. The use of two cooling circuits provides
greater -e*ibility in manipulating absorption conditions in the
column. The tail gas leaves the column at about 10%&. Kea" acid
from the coolercondenser is added to an appropriate tray midway
up the column, and ma"eup water at +%& is added to the top tray.
 The acid drained from the bottom of the column contains some
dissolved nitrogen o*ides.

14. S7- C+=*

 The bleaching column is a smaller sieve traytype column. 6mpure


acid runs down the column from the top tray and air is bubbled up
through the li@uor to remove dissolved nitrogen o*ides. The acid
from the base of the column is the 8nal desired 30 Awt.C
product.

15. S7+-) T< 


 

(0

  'tores the supply of nitric acid produced from the process


plant.

CHAPTER SIX
EUIPMENT DESIGN

 The need to design process e@uipment may arise as a result of 


the desire toE

i. ?odify an e*isting process e@uipment or


ii. 7evelop new e@uipment.
 

(1

?odi8cation of e*isting e@uipment may be re@uired as a result of 


poor performance or the need of scale up Aor downC. )or e*ample,
increased mar"et success of a product may lead to increased
production. 6t may be more economical to increase the capacity of 
the e*isting e@uipment rather than add another line of 
e@uipment. This is usually the case when operational cost costs
Aman power, energy etc.C are high.

;ew e@uipment, on the other hand may be desired as a result of 


successful laboratory research and pilot plant studies or as a
result of satisfactory process simulation using the computer.

6n either situation Anew or e*isting e@uipmentC, the actual design


commences with the assessment of the characteristics of the feed
materials, the products and the physical and chemical processes
re@uired to convert the raw material to products. The overall
satisfactory performance and reliability of the e@uipment would
depend on the following factors.

6. Optimum processing conditions


66. <ppropriate materials of construction
666. 'trength and rigidity of components
6U. 'atisfactory performance of mechanical part
U. eliable methods of fabrication
U6. /ase of maintenance and repairs
U66. /ase of operation and control.
U666. 'afety re@uirements
6R. /nvironmental impact

 The typical process e@uipment design procedure will involveE

1. 'pecifying the problem


 

(2

2. <naly!ing the probably solution


#. Preliminary design, applying chemical engineering process,
principles and theories of mechanics relevant to the
problem.
4. 'electing appropriate materials of construction.
$. /valuating and optimi!ing the design, the possible
application of computer aided design A&<7C system li"e
:Y'6', <spen Plus etc
3. Preparing the drawings and speci8cations
%.1.PROBLEM SPECIFICATION

 The speci8cation of the problem is the "ey stone in the @uest to


design an e@uipment to meet the needs of the customer.
'peci8cation of a problem may includeE

1. The @uantity of material to be processed in a given time


such as the proposed capacity of the e@uipment.
2. The physical and chemical properties of the product.

&onstraints such asE

a. <vailability and cost of materials of construction


b. <vailability and cost energy, water, oil etc.
c. Dudget for production
d. <vailability and cost of manpower with relevant s"ill for
fabrication
e. 'pace to be occupied by the e@uipment
f. /nvironmental issues
g. 'afety issues
h. ;umber of wor"ing days in the year
i. /rgonomics
 

(#

%.2.ANALY@ING THE PROBLEM SOLUTION

< thorough analysis will reduce the list for e*ample if the
e@uipment is to be used for small scale processing. <ll the
constraint listed above will need to be considered.

%.3.PRELIMINARY DESIGN5 APPLYING CHEMICAL


ENGINEERING
PROCESS PRINCIPLE AND THEORIES OF
MECHANICS.

Probably the most important e*pression in the design of process


e@uipment is that of mass and energy balance which may be
e*pressed in general term asF

6nput N generation  output  consumption [ accumulation

 This e*pression is found in various forms in thermodynamics, -uid


mechanics, transport phenomena, heat transfer, separation
process and other sub5ect areas. 6t is simply an e*pression of 
indestructibility of matter and energy. This e*pression applies to
all raw materials, intermediate and product.

%.4 MATERIAL SELECTION

?aterials are critical in the design of process e@uipment. ?aterials


must be selected to ta"e care of possible corrosion problems.
?aterials of construction should also possess ade@uate
mechanical properties to withstand tensile, compressive, shear
and impact stresses.
 

(4

'tainless steel of various grades 8nds wide application in process


e@uipment design especially for parts in contact with raw
materials and product. Hlass, plastic and rubber lined vessels are
also used are also used when materials tend to react with steel.
'teel of various carbon contents are used for compounds such as
shaft, springs and gears and for support structure.

%.# DESIGN OPTIMI@ATION

 The calculation process in the design of e@uipment may re@uire


simple arithmetic, algebraic, diJerential calculus or integral
calculus. 6n many cases an e*act solution may not be feasible
thus necessitating the use of various appro*imation techni@ues
such as graphical or numerical methods.

6n many cases also, only some parts of the e@uipment are


designed on the basis of analytical calculations. Practical
conditions are used to determine the speci8cations of the
remaining part. 6t is thus not unusual to have several feasible
solutions. There is thus the need to select the best solution. The
ultimate goal is to minimi!e cost or ma*imi!e pro8t.

6n chemical process industries, e@uipment used are classi8ed into


twoF Proprietary e@uipment such as pumps, centrifuges which are
designed and manufactured by a specialist 8rm.

 ;on proprietary e@uipment such as reactors, heat e*changers,


condenser, bleaching vessels etc are designed as specially
re@uested.
 

($

%.% SUMMARY OF THE DESIGN AND SPECIFICATION


OF EUIPMENT CALCULATION.

6n designing and specifying of e@uipment for chemical industries,


the variables parameters involved namelyF pressure,
temperature, density, volume, area, diameter, height, heat duties,
heat capacities etc must be carefully calculated. This gives the
designer e*act data for fabrication and manufacturing. )or the
production of ;itric <cidF the following e@uipment are designed
and speci8edF ;itric <cid storage tan", <mmonia storage tan",
<bsorber, &onverter, O*idation vessel, heat e*changers.

  FOR REACTORS
 The operating intensity is given for the
reactors[112>3.#24"gm224hrs

[112>3.#24"gm2day

/@uipment ?ass of  <reaAm2C 7iameterAmC


reactant A"ghC
&onverter 1#$00 2(.3( 3.04
O*idation 2##20 4>.$$ +.>4
Uessel
<bsorber ##$#0 +1.24 >.$2
 The stripper column has 10 plates

  FOR STORAGE TANKS

/@uipment Type ;itric <cid storage


tan"
 

(3

'hape &ylindrical
 ;ature 6nsulated
?aterial of  'tainless 'teel
&onstruction
&apacity $0000000"ghr
UolumeAm#C 2#.(
7iameterAmC 4.3
:eightAmC 1#.>

/@uipment Type <mmonia 'torage tan"


 'hape &ylindrical
 ;ature 6nsulated

?aterial of &onstruction 'tainless 'teel


 &apacity 1#$3$"ghr
UolumeAm#C 33.(
7iameterAmC 3.$
 :eight AmC 1>.3

  FOR HEAT EXCHANGERS

=sing the formulaeF \[<=7Tm


<[ \=dTm
Khere
\[ :eat 7uty of the heat e*changerAGKC
<[ areaAm2C
=[ Overall :eat Transfer &oecientAGKm2CA This is assumed for
allC
7Tm[9og ?ean Temperature 7iJerenceA&elsiusC
 

(+

=sing a countercurrent -owF 7T?[ 7T1 −¿ 7T2 lnA7T1 7T2C

7T1 [ ThinTcout
7T2 [ Thout T&in
/@uipment \ AGVhrC Thin Thout T&out Tcout
Kaste :eat Doiler A1C 1$>+32$2(>0 2$0 #0 410
<ir :eater #$0 200 1$0 2$0

'tac" +4#2# 200 1$0 #0 11(.$


Has
:eater
Kaste 14>+(1.4 20( $0 1$0 #2
:eat
DoilerA2C
;:# 44#+.($ 410 ##0 23.3 2(.2
'uper
:eater
;:# 14>+(1.4 20( 13+.2 2(.2 ##.4
Uapori!er

 Table 3.1E Table showing the heat transfer area of some


e@uipment

/@uipment \AGK'C <reaA?2C


'tac" Has :eater 20.3$ 2
Kaste :eat DoilerA1C 44#+.($ 1#0.$
Kaste :eat DoilerA2C 41.31 11.(#
;:# 'uper :eater 44#+.($ 12+.3
;:# Uapori!er 41.31 1.(+
<ir :eater 41##.+ $((.+
 

((

CHAPTER SEVEN
PROCESS CONTROL AND INSTRUMENTATION

6nstruments are provided to monitor the "ey process variables


during plant operation. They may be incorporated in automatic
control loops, or used for the manual monitoring of the process
operation. They may also be part of an automatic computer data
logging system. 6nstruments monitoring critical process variables
will be 8tted with automatic alarms to alert the operators to
critical and ha!ardous situations.
  6t is desirable that the process variable to be monitored be
measured directlyF often, however, this is impractical and some
dependent variable, that is easier to measure, is monitored in its
place.
&.1 OB"ECTIVES
 The primary ob5ectives of the designer when specifying
instrumentation and control schemes areE
1. 'afe plant operationE
AaC To "eep the process variables within "nown safe operating
limits.
AbC To detect dangerous situations as they develop and to provide
alarms and automatic shutdown systems.
AcC To provide interloc"s and alarms to prevent dangerous
operating procedures.
2. Production rateE To achieve the design product output.
 

(>

#. Product @ualityE To maintain the product composition within the


speci8ed @uality standards.
4. &ostE To operate at the lowest production cost, commensurate
with the other ob5ectives.
 These are not separate ob5ectives and must be considered
together. The order in which they are listed is not meant to imply
the precedence of any ob5ective over another, other than that of 
putting safety 8rst. Product @uality, production rate and the cost
of production will be dependent on sales re@uirements. )or
e*ample, it may be a better strategy to produce a better@uality
product at a higher cost.
6n a typical chemical processing plant these ob5ectives are
achieved by a combination of automatic control, manual
monitoring and laboratory analysis.
&.2 PLANT CONTROL CONFIGURATION
 The plant will be designed for manned operation and will be lin"ed
to the ad5acent fertili!er manufacturing plant. &ertain
con8gurations will be put in place to monitor some "ey
parameters of the plant.
 The acid plant process control will be embedded in the plant 7&'.
 The instruments of the individual process units will be terminated
in 5unction bo*es located at the units s"id limits. )rom here these
instruments will be connected to instrument cabinets in the
au*iliary room and integrated in the P<'.
 The plant safety instrument system A'6'C will be independent of 
the P<'. There will be a lin" between the P<' and the '6' for data
 

>0

monitoringlogging and maintenanceoperational override control


purposes. )ire and gas monitoring will also be a dedicated module
integrated in the safeguarding system.
 The process control schemes of some vital units are discussed as
followsE
A?!+-7+ +=*

 The process control scheme for the absorption column is


presented in 8g 6t was designed from the recommendations
presented in the :<BOP analysis.

6t features ratio control on the ma"eup water stream. The signals


from -ow transmitters on this line and on the gas input line are
fed to the ratio controller, whereby the ma"eup water stream is
ad5usted.
Other control features include a pressure controller on the tailgas
outlet stream so that the column absorption pressure can be
maintained at the design operating value of >$0 "Pa. <
temperature transmitter on the tailgas outlet stream provides the
signal for control of the overall coolingwater -ow rate. This is the
temperature which is most useful in determining good absorption.
 The cooling circuit itself is fed from a common line Aon which the
overall -ow rate is controlledC. 'mall bloc" valves on each of the
tray coolingcoil feed lines enable -ow rate regulation to each of 
the coils. These valves feature a removable top whereby a
magnetic -ow meter may be inserted to read the -ow rate. The
valves need only be set initially and then periodically ad5usted
manually.
 

>1

 There is no automatic control on the -ow rate of the gas inlet


stream or wea"acid condensate stream, since both of these -ows
are predetermined by feed -ow rates earlier in the process.
6solation valves and provision for spectacle blinds are included to
enable the column to be isolated during shutdown periods.
 The productacid solution is withdrawn from the column using a
level control valve on this line. The li@uid level in the base of the
column must be maintained slightly above the level of the plate
downcomer to prevent incoming gas from bypassing the sieve
plates.
<ll controllers suggested for the absorption column feature :6H:
and 9OK alarms for good control.
 The 8nal safety re@uirement is a relief line with a relief valve
protected by a bursting disc.
A- /)7)-
 The process control scheme suggested for the air heater is shown
in )ig. This -ow scheme features a control valve on the
compressed air inlet line. < temperature controller ta"ing its
signal from the heater outlet line ensures the -ow is regulated to
maintain the heater temperature of 2$0%&. <ir pressure is
controlled prior to entry into the unit and is "ept constant at +.#
atm.
< pressure indicator on both inlet and outlet steam lines enables
this parameter to be ade@uately monitored.
 

>2

 The nitrogen o*ide reaction gas stream cannot be directly


controlled from the air heater. 6nstead the -ow rate, temperature
and pressure are predetermined by the reactor feed conditions.
Doth inlet and outlet lines possess isolation valves for plant
shutdown. These lines would be blan"ed before any platinum
recovery wor" was attempted on the heater. 6nlet and outlet lines
also feature temperature indicators, consistent with the policy of 
constant monitoring of this parameter throughout the process.
  A**+ V+-!)- 6 S=)-/)7)-
Pressure indicator and controller will be installed to maintain
ammonia vapor at +.# atm. Temperature indicator and controller
is re@uired to ensure that the outlet temperature of 2$0%& is
achieved in the superheater. The control scheme is shown in the
8gure below.
  A**+ C+8)-7)-
 Temperature control system is needed within the converter to
ensure that the temperature in the converter does not drop below
the reaction temperature of (>0>00%&, to avoid loss of heat.

&.3 ALARMS, SAFETY TRIPS AND INTERLOCKS


<larm systems need to be installed in speci8c areas to alert
operators of serious, and potentially ha!ardous, deviations in
process conditions. Gey instruments are 8tted with switches and
relays to operate audible and visual alarms on the control panels
and annunciator panels. Khere delay or lac" of response, by the
operator is li"ely to lead to the rapid development of a ha!ardous
 

>#

situation, the instrument would be 8tted with a trip system to ta"e


action automatically to avert the ha!ardF such as shutting down
pumps, closing valves, operating emergency systems.
 The basic components of an automatic trip system areE
1. < sensor to monitor the control variable and provide an output
signal when a preset value is e*ceeded Athe instrumentC.
2. < lin" to transfer the signal to the actuator, usually consisting
of a system of pneumatic or electric relays.
#. <n actuator to carry out the re@uired actionF close or open a
valve, switch oJ a motor.
 The hightemperature alarm operates a solenoid valve, releasing
the air on the pneumatic activator, closing the valve on high
temperature.
&.3.1 INTERLOCKS
Khere it is necessary to follow a 8*ed se@uence of operations for
e*ample, during a plant startup and shutdown, or in batch
operations interloc"s are included to prevent operators departing
from the re@uired se@uence. They may be incorporated in the
control system design, as pneumatic or electric relays, or may be
mechanical interloc"s. Uarious proprietary special loc" and "ey
systems are available.
 Table +.1E 9etter &ode for 6nstruments 'ymbols
Property )irst letter 6ndicating only &ontrolling

measured only
)low  rate ) )6 )&
9evel 9 96 9&
Pressure P P6 P&
 

>4

 Temperature T T6 T&
:umidity : :6 :&
6 6ndicator &  &ontroller
9 9evel T  Temperature
) )low rate P  Pressure
: :umidity
ASource: Sinnott, R.R 1999).
&.4 LINING, PIPING, VALVES AND PUMPS

6n )ig.+.1, which is the piping and instrument diagrams, there are


various mechanical component introduced in the plant to obtain
ma*imum eciency some of which includes, -anges, valves,
piping lines, blinds, gas"ets and so on.

&.4.1 VALVES

 The valves used for chemical process plant can be divided into
two broad classes, depending on their primary functionE

• 'hutoJ valves Abloc" valvesC, whose purpose is to close oJ 


the -ow.
• &ontrol valves, both manual and automatic, used to regulate
-ow.
 The table below shows some of the valves used in the P and 6
diagram A8gure $C, their symbols, and functions.

 Table +.2E Types of Ualves and 'ymbol =sed 6n P67

NAME SYMBOL FUNCTIONS


 

>$

&ontrol
=sed to control -ow in lines.

<utomatic )itted on sensitive lines and are


either pneumatically or digitally
controlled.

&hec"

)itted in lines of relatively high


pressure or velocity

Dutter-y

=sed for control of gas or vapour


-ows

&.4.2 "OINTS

 There are various 5oints used in 8g #.0 either as -ow reducers, or


to aid the carrying property of pipe. <nd eJective transport of 
-uids in the piping -ow. Delow is a table of the various elbows and
 5oints used in the P and 6 diagramE
 

>3

 Table +.#E Voints

 "OINTS SYMBOLS FUNCTIONS


AND
ELBOWS
/\=<9 IT =sed to reduce a -ow
/7=&/ VO6;T line into three e@ual
lines

=sed in 5oining a

>0o  T  running line to a -ow

&O;;/&TO line.

=sed in channeling lines


also reduces -ow
/9DOK
speed.

=sed in channeling lines


in pipe support.
9O;H  <76='
/9DOK

=sed in branching lines.

4$o 9<T/<9

=sed in reducing
pressure -ow.
 

CHAPTER ' >+

SAFETY AND
  ENVIRONMENTAL
CONSIDERATIONS
/7=&/

'.1 SAFETY 

'afety is the condition of being protected against any danger.


/very organi!ation has a legal and moral obligation to safeguard
the health and welfare of its employees and the general public.
&.# PIPE SUPPORT
 The good management practices needed to ensure safe operation
 The 7esign
will also of a plants
ensure P and 6operation.
ecient is not complete
6n a without
chemicaltheprocessing
use of 
supports. Pipe
industry, thesupports in plant
chemicals usedpiping helps in can
or produced reducing cost and to
be ha!ardous
number of or
humans pump re@uired to maintain
the environment line -ow
if not properly parameter
handled and thisand
could
safety of personnel
e@ually through
lead to a lot operation
of damage !one. and 8nancially.
structurally

Delow
 The is some
best ma5or type are
organi!ations of supportE
those that have come to the reali!ation
that provision of safety is not only the right thing to do for their
6  D/<? 'upport to carry pipe lines
employees, it is also pro8table.
:  D/<? 'upport above 2m
  A687)! +  !) +-< )8-+*)7
=  &:<;;/9
1. =ltimately, safety leads to more pro8t as less money is spent
P9<T/' ta"ing
TO <96H; U<9U/'
care of legal bills, hospital bills, and repair of 
e@uipment.
':O/' TO :O6'T P6P/ 6;TO POP/ O6/;T<T6O;
2. 6t gives the company a good name.
#. :appy employees which increases their 5ob performance.

'afety is usually considered in three classesE

6. 'afety of the environment


66. 'afety of the personnel
666. 'afety of the plant and e@uipment.
 

>(

 The term Sengineering safety covers the provision in the design


of control systems alarms, trips, pressure relief devices, automatic
shutdown system and duplication of "ey e@uipment, 8re8ghting
e@uipment and serviceF personnel protect e@uipment and so on.
 

>>

'.1.1 SAFETY OF THE ENVIRONMENT

 There are several ha!ards associated with industrial process.


 These ha!ards need to be prevented and "ept in chec" in order to
protect the environment. /nvironment in this conte*t refers to the
immediate surroundings around the plant. )or the safety of the
environment to be ensured, the following points should be noted
and appliedF

1. )laring of gases should be done minimally.


2. The level of to*icity of e]uent should be monitored regularly
and "ept in chec".
#. 'torage tan"s should be situated in areas away from vehicle
trac.
4. The control room should be attended to at all times to
ensure that there is an immediate response if an alarm is
triggered.
$. There should be a way of informing the community around
the facility if there is danger that might aJect them e.g )ire.
<n alarm is suggested, and this should be tested regularly.
3. Protect pipe rac"s and cable trays from 8re.
+. )ire8ghting system must be provided within the comple*.
 This consistE
 )ire water pipe networ" throughout the facility supported by
necessary hydrants. :oses should be permanently placed
near these hydrants.
 The system should have a suitable water pump. 6t is advised
that there be at least 2 pumps. One big one to 8ll the lines or
pump large volume of water into it Awhen the water is being
depleted very fast li"e in a case of 8reC and a smaller 5oc"ey
 

100

pump to maintain the pressure in the line. 6t would start


more fre@uently than the big pump.
 6t is suggested that the system should have its own separate
standby generator.
 )ire entry suits and other protective clothing, compressed air
breathing apparatus and 8re blan"ets should be made
available in every building.

'.1.2 SAFETY OF THE PERSONNEL

 The personnel of a company refers to the operators and staJ of 


that company who ensure that the production process move on
smoothly. Their safety can be ensured in the following was.

1. Provision of personal protective e@uipment APP/C and


ensuring that they are properly used.
2. Pipes and e@uipment that contain very hot li@uids for
e*ample the heater must be lagged to ma"e sure it does not
cause in5ury to personnel.
#. <ll chemicals in the plant must be properly label with its
chemical ha!ard identi8cation chart and their ?aterial
'afety 7ata 'heet A?'7'C must be available and updated
regularly also.
4. )irst aid "its must be provided in all buildings.
$. /mergency means of transportation must be provided in
case of any accident.
3. /mergency e*it doors must be provided and these e*its
clearly mar"ed for all to see.
+. &leanliness of the facility must be ensured at all times to
avoid unnecessary ris" or accident.
(. 'mo"ing should be avoided in process area.
 

101

>. )ire e*tinguishers must be made available at strategic


points within the facility.
10. <ll ladders must have hand rails and personnel encouraged
to use them whenever climbing.
11. 'afety signs and symbols should be placed at ha!ardous
area.

'.1.3 SAFETY OF THE PLANT AND EUIPMENT

< plant includes any machinery, e@uipment Aincluding scaJoldC,


appliance, implement or tool and any associated computer or
8tting used in the production process of a material or substance.
 There are diJerent types of ris"s associated with using diJerent
types of e@uipment. To mitigate this ris", the following must be
doneE

1. <s ;itric acid is "nown to be highly corrosive, regular


pigging of the pipelines with both smart and scraper pigs
should be conduct so as to chec" this.
2. &orrosion protection is achieved by the well proven use of 
suitable austenitic stainless steel where condensation can
occur and by regular monitoring of the conditions.
#. egular maintenance of e@uipment should be carried out.
4. &hec" to ensure that e@uipment and machineries meet
health and safety standards before it is purchased.
  REACTOR
eactor is a vessel in which chemical transformation ta"es place.
 The converter, o*idi!ing unit and absorber are the reactors in this
design. The catalytic reactor is designed to give a uniform
distribution of the airammonia mi*ture over the catalyst gau!es.
 

102

?aintenance of the catalyst operating temperature is very


important for the ;O yield. This is achieved by ad5usting the
airammonia ratio and ensuring that the lower e*plosive limit for
ammonia in air is not e*ceeded. The following safety steps should
be followed in the design and operation of the reactor.

 The materials going into the reactor must be puri8ed. This is


done to remove impurity that will aJect the reactor.
 The reaction condition i.e. temperature, pressure etc must
be monitored closely.
 The reactor should be cleaned accordingly during periodic
maintenance.

  COMPRESSOR
Khile operating the compressor, the following precautions should
be observed.

 The air must be dried properly to avoid water entering into


the compressor which could damage it.
 The air must be 8ltered properly to avoid foreign particle
from entering into the compressor.
 The proper operating pressure should be maintained at all
times.
 &oolant must be chec"ed regularly and topped.
 6n case of shut down, the shut down and start up procedures
should be strictly adhered to.
  HEAT EXCHANGERS
)or heat e*changers to wor" eJectively and safely, the following
must be implemented.
 

10#

 /nsure that the heat e*changer is pressure tested as


designed.
 /nsure that it is cleaned periodically and faults and lea"age
recti8ed if found. 6nspect after cleaning before coupling
bac".
 The water must be puri8ed especially the one going into the
boiler to remove chlorine because ignition occurs when
chlorine is passed into ammonia forming nitrogen and
hydrochloric acid and if chlorine is present in e*cess, then a
highly e*plosive nitrogen trichloride A;&l#C is formed. <s we
cannot guarantee 100 conversion of ammonia in the
converted and no lea" in the boiler, the water should be
puri8ed.
  PUMPS
)or the pumps to wor" eJectively and safely, the process
operators should ensure thatF

 The right operating temperature and pressure must be used.


 There should be a minimum -ow line that helps to maintain
a certain rate of -ow in the pump preventing it from going
into cavitation.
 9ube oil to gland bearings is available, bottle 8lled and ready.
 The lube oil should be changed at regular intervals.
 The vents should be properly cleaned and capped
 There should be no particle or foreign body in both the
suction and discharge lines.
  TANKS
;itric acid is normally stored in -at bottomed, roofed tan"s, made
from low carbon austenitic stainless steel, installed in areas
 

104

provided with suitable containment facilities. The acid level in the


tan" is monitored by means of a level indicator. < vent to the
atmosphere allows the escape of gas which comes from li@uid
movement and thermal eJects. 6t is normal to earth the tan"s. )or
the life span of the tan"s to be preserved, the following should be
doneE

 The tan" should be cleaned regularly


 Periodically, the tan"s should be chec"ed for corrosion and
the aJected part could be painted.
 The right operating conditions for the tan"s must be
maintained.

'.1.4 GENERAL SAFETY PRECAUTION

Henerally, precaution is ta"en to prevent accidents or ha!ards Aa


potential dangerC. :a!ards can either be intrinsic or e*trinsic.
6ntrinsic ha!ards are naturally occurring ha!ards caused by wind,
earth@ua"e, lighting and water. The eJects of intrinsic ha!ards
include lea"age in pipes, e*plosion of pipes, collapse of 
production buildings, rupture of welded 5oints etc. the following
precautions can be ta"en to mitigate the dangers posed by
intrinsic ha!ardsE

• 9ightning rods should be installed at strategic points.


• 7rainages should be wide and deep enough, and should also
be channeled properly to prevent -ooding with the facility.
• /*plosive substances have to be stored in a cool dry place
away from sunlight and ultraviolet rays.
 

10$

•  The -oor around the industry should be properly cast around


with concrete or other weather resistant covering and the
road networ"s properly tarred

 /*trinsic ha!ards are manmade ha!ards caused by man due to


carelessness.They may include dropping of an oil 8lter on the
-oor, igniting -ame close to a -ammable substance, not "nowing
how to operate a machine or e@uipment, ignoring procedure for
starting or using e@uipment, using wrong tools. They can be
prevented by the following measuresE

• Personnel coming into the facility for the 8rst time must be
given a proper safety orientation on the dos and donts of 
the company policy on safety and regular safety tal"s on
safety and maintenance of plant must be conducted.
• egular training of personnel on safety issues should also
ta"e place.
• Hood house"eeping practice by all employees should be
encouraged.

'.2 HA@ARD OPERABILITY :HA@OP; STUDY 


:a!ard and operability study sometimes simply referred to as
operability 'tudies, provide a systematic and critical
e*amination of the operability of a process. They indicate
potential ha!ards due to deviations from the intended design
conditions.

'.2.1 BASIC PRINCIPLES


 

103

< formal operability study is the systematic study of the design,


vessel by vessel, and line by line, using Sguide words to help
generate thought about the way deviations from the intended
operating conditions can cause ha!ardous situations.

 The following words are also used in a special way, and have
the precise meanings given belowE

^ I7)7+E the intention de8nes how the particular part of 


the process was intended to operateF the intention of the
designer.

^ D)87+!E these are departures from the designers


intention which are detected by the systematic application of 
the guide words.

^ C=!)!5 reasons why, and how, the deviations could occur.


Only if a deviation can be shown to have a realistic cause is it
treated as meaningful.

^ C+!)=))!5 the results that follow from the occurrence


of a meaningful deviation.

^ H-6!5  conse@uences that can cause damage AlossC or


in5ury.
 

10+
 

10(

 Table (.1 :<BOP 'T=7YE Kea"acid condensate stream

7eviation Possible conse@uences &onse@uence <ction e@uired


;o )low 1.Pump )ailure 7e8cient @uality product aC 6nstall 9OK 9/U/9 <9<?
and high ;O* tail gas on 96& at the base of the
emission levels. absorption column.
2. Ualve fails shut. <s for 6 &overed by aC.
Ualve overheats. bC 6nstall "ic"bac" on pumps
#. 9ine fracture <s for 6 and 2. &overed by aC and bC.
cC egular inspection and
patrolling of wea"acid
transfer lines and seals.
?ore )low 4. :igher humidity in :igher ma"e but wea"er dC 6nstall a :6H: 9/U/9
feed air. product acid. <9<? on 96& at the base of 
the absorption column
?ore Temperature $. high feed rate causing Possible higher ;O* 'ee Table (.3.
larger heat of reaction emission.
?ore Pressure 3. 6solation valve is 9ines sub5ect to full &overed by bC
closed in error while delivery pressure fC Perhaps worthwhile
pump running. installing a pressure gauge
upstream of the delivery
pump
+. Thermal e*pansion on Possible line fracture or gC Provide thermal e*pansion
the isolation. -ange lea"age relief in the
Ualve section.
9ess )low (. )lange lea"age or 7ecreased absorption. &overed by aC, cC, and dC.
valve 9ower product ma"e
stub blan"ed but lea"ing
9ess Temperature >. eaction gas 6ncreased dissolved ;O* 'ee Table (.3.
temperature in o*idation concentrations in
 

10>

unit lower. product acid.


?aintenance 10. /@uipment failure, Process stops. /nsure all pipes and 8ttings
-ange lea", catalyst are constructed of the right
changeover in reactor, materials and arc stress
etc. relieved.

 Table (.2 :<BOP studyE ?a"eup water feed stream.

7eviation Possible causes conse@uences <ction e@uired


;o )low 1.Pump )ailure 7e8cient @uality product aC 6nstall 9OK 9/U/9 <9<?
and high ;O* tail gas on 96& at the base of the
emission levels. absorption column.
2. Ualve fails shut. <s for 6 &overed by aC.
Ualve overheats. bC 6nstall "ic"bac" on pumps
#. 9ine fracture <s for 6 and 2. &overed by aC and bC.
cC egular inspection and
patrolling of wea"acid
transfer lines and seals.
?ore )low 4. &ontrol valve fails open 7ilute acid product is dC 6nstall a :6H: 9/U/9 <9<?
formed on
96& at the base of the absorption
column
?ore Temperature $. :igher feed temperature Possible higher ;O* 'ee Table (.3
to the emission due to lower
efrigeration unit. absorption. eC /nsure refrigeration unit is
3. )ailure in the <s for $. well
refrigeration unit. maintained with ade@uate
 

110

control
?ore Pressure +. 6solation valve is closed 9ine sub5ect to full delivery &overed by bC.
in error whilst pump pressure. 6V Perhaps worthwhile installing a
running. pressure gauge upstream of the
delivery pump.
Possible line fracture or gC Provide thermal e*pansion
(. Thermal e*pansion in -ange lea"age relief in the valve section.
the isolation valve section
A8reC.
9ess -ow >. )lange lea"age or valve 7ecreased absorption. &overed by aC,cC and dC
stub blan"et but lea"ing :igher operating cost in
lost water
9ess Temperature 60. eaction gas 6ncreased dissolved ;O* 'ee Table (.3
temperature in o*idation concentrations in product
unit lower. acid.
?aintenance 11. /@uipment failure, Process 'tops /nsure all pipes and 8ttings are
-ange lea", catalyst constructed of the right
changeover in reactor, etc . materials and are stress relieved.

 Table (.#. :<BOP studyE Hasinlet stream

7eviation Possible causes conse@uences <ction e@uired


 

111

;o )low 1.)low stopped upstream ;o absorption in column. aC /nsure li@uid feeds to


/ntire process stops as tail absorber and other process
gas ow stops. unit shut down.
bC 6nstall 9OK )9OK
<9<? on )6&.
2. 9ine bloc"age or the <s for 6. &overed by aC and bC.
isolation valve shut in error. Pressure buildup in pipe cC 6nstall "ic"bac" on
and secondary upstream pumps and
#.9ine fracture  <s for 6. ensure pressure relief 
Hases escape into the system is ade@uate
surroundings. dC /nsure regular patrolling
of feed transfer lines.
eC Plant emergency
shutdown procedures
?ore )low 4. 6ncreased feed Possible reduction in )C atio control on the
absorption li@uid feed streams should
/ciency. be sucient.
?ay cause -ooding. gC 6nstall :6H: 9/U/9
<9<? on the )6&.
?ore Pressure $.)looding =nit sub5ect to high &overed by cC.
pressure, bursting discs hC /nsure correct si!ing on
may rupture, tail gas pressure relief system.
3. 6solation valve release. &overed by bC and cC.
accidently closed <s for 2.   iC Provide for thermal
+. Thermal e*pansion in 9ine fracture or -ange e*pansion relief in the
isolation. lea"age. design of the isolation
valve section
?ore Temperature (. 6nsucient cooling 7ecreased absorption,  5C /nsure accurate
higher pollution. temperature control on the
internal cooling circuit.
9ess -ow >. 9ea"ing inlet range <s for #. &overed by bC, and dC
9ess Temperature 10. Overcooling. 6ncreased dissolved gasses &overed by 5C
 

112

in acid.
: i g h ;O* composition 11. 6mproved yield from :igher tailgas emission "C ?anually increase ma"e
reactor. levels possible. up water &omposition -ow
rate.
 Table (.4. :<BOP studyE Has  Outlet stream.

7eviation Possible causes conse@uences <ction e@uired


;o -ow 6. ;o inlet gas -ow. ;o tail gas for e*pansion. 'ee Table (.1.
Pressure build up in column aC 6nstall 9OK 9/U/9
and line <9<? on P6&.
2. )looding in column. <s for 6. bC 6nstall pressure relief 
valve with bursting disc.
&overed by bC.
#. P&U fails shut, line <s for 2. cC 6nstall :6H: 9/U/9
bloc"age or isolation valve <9<? on P6&.
closed in error. &overed by aC
<s for 1. dC 6nstitute regular
4. 9ine fracture or -ange inspection of all transfer
failure lines.
?ore -ow $. 6ncreased gas feed at  Transfer line sub5ect to &overed by bC and cC.
inlet. higher pressures. &overed by bC and cC.
<s for $. dC 9oo" to altering ma"eup
3. 7ecreased ;O*  Tailgas emission levels up. water feed rate in
absorption response.
?ore Temperature +. :igher feed gas or li@uid 7ecreased absorption and eC 6nstall :6H: 9/U/9
inlet temperature. higher ;O* emission. <9<? on T6&
?ore pressure. (. <ll of $, 3, andor +. <s for $, 3, and +. &overed by bC and cC.
>. Thermal e*pansion in 9ine fracture or -ange fC 6nstall thermal e*pansion
isolation valve section lea"age. relief in isolation valve
A8reC. section.
10. P&U fails shut or <s for # &overed by bC and cC.
isolation valve shut in error.
 

11#

9ess -ow 11. 9ea"ing -ange or valve 9ess tail gas for e*pansion &overed by aC and dC.
stub not blan"ed and and release of ;O* to the
lea"ing. environment.
12. )looding.
9i@uid &arryover 1#. The entrainment device &ondensation is down, eplace entrainment
ineJective. steam lines AcorrosionC. device.
?aintenance 14. /@uipment failure, Process stops. /nsure all pipes and 8ttings
-ange lea", catalyst are
changeover in reactor, etc . constructed of the right
materials and are stress
relieved

 Table (.$ :<BOP studyE 9i@uidoutlet stream.

7eviation Possible causes conse@uences <ction e@uired


;o -ow. 6. ;o li@uid inlet from either 'ee Tables >.3 and >.+
ma"eup water or acid aC &overed by control and
condensate. alarms speci8ed in Tables (.1,
2. )looding in column. 6ncrease in column pressure. (.2 and (.#.
9i@uid level in column &overed by aC.
increases adding to -ooding bC 6nstall :6H: 9/U/9 <9<? on
problems. 96&.
#. 9&U fails shut. cC egular patrolling and
7ischarge of acid into the inspection of transfer lines.
4. 9ine fracture.4. 9ine fracture. surroundings. dC 6nstall suitable alarms to
9oss of feed to the stripping stripping
column column to indicate loss of -ow
?ore -ow $. 9&U fails open. Has begins to bypass the eC 6nstall 9OK 9/U/9 <9<? on
plates causing higher ;O* 96&.
emissions.
 

114

?ore temperature 3. :igher inlet temperatures 9ess dissolved ;O* in acid &overed in Tables (.1, (.2 and
but higher ;O* tailgas (.#.
emissions
?ore pressure +. 9&U fails shut or isolation 9ine sub5ect to full surge or &overed by aC
valve close in error. delivery pressure.
9ess -ow (. 9ea"ing -ange or valve stub 9oss to surrounding. &overed by dC and eC
not blan"ed and lea"age.
9ess temperature >. 9ower inlet stream :igher concentrations of  'ee Tables (.1, (.# and (.4.
temperatures or over capacity dissolved ;O* in product
from cooling circuit. acid.
;O* dissolved 10. 9ower steam temperature. :igher downstream 'ee Tables (.1,(.# and (.4
operating costs.
'ame as >.
maintenance 11. /@uipment failure, -ange Process stops /nsure all pipes and 8ttings are
lea", catalyst changeover i n constructed of the right
reactor, etc. materials and are stress
relieved
 

11$

 Table (.3E :<BOP studyE coolingwater circuit.

7eviation Possible causes conse@uences <ction e@uired


;o )low 1.Pump )ailure :igh emissions of ;O* in aC 6nstall :6H: 9/U/9 <9<? on
tail gas.  T6& on the tailgas outlet line to
indicate high emissions.
2. Ualve fails shut. &overed by aC.
<s for 1 bC 6nstall "ic"bac" on pumps.
#. 9ine fracture Ualve overheats. &overed by aC and bC.
<s for 1 and 2 cC egular inspection and
patrolling of 
coolingwater circuit lines and
associated
?ore -ow 4. &ontrol valve fails open. Product acid is at lower dC 6nstall a 9OK 9/U/9 <9<? on
temperature therefore,  T6& on the tail gas outlet line
higher dissolved ;O*.
?ore temperature $. :igher feed temperature Possible higher ;O* &overed by aC
to the refrigeration unit. emissions due to lower eC /nsure refrigeration unit is
absorption. well
<s for $. maintained with ade@uate
control
?ore pressure +. 6solation valve is closed 9ines sub5ect to full &overed by bC.
in error while pump delivery pressure. fC Perhaps worthwhile installing a
running. Possible line fracture or pressure gauge upstream of the
(. Thermal e*pansion in -ange lea"age. delivery pump.
the isolation valve section   gC Provide thermal e*pansion
A8reC. relief in the valved section
9ess -ow >. )lange lea"age or 7ecreased absorption. 9ow &overed by aC, cC, and dC.
valve stub blan"ed but @uality product and high
lea"ing emissions.
9ess Temperature 10. :igher duty from 6ncreased dissolved ;O* &overed by aC, cC, and dC.
 

113

refrigeration unit. concentration in product


acid.
?aintenance 11. /@uipment failure, Process stops /nsure all pipes and 8ttings
-ange lea", catalyst are constructed of the right
changeover in reactor , etc materials and are stress relieved
 

11+

'.3 ENVIRONMENTAL IMPACT ASSESSMENT :E.I.A;

 This is the assessment of the possible positive and negative


impact that a proposed pro5ect may have in the environment,
together consisting of the environmental, social and economic
aspect. 6t is a systematic process of identi8cation, prediction
evaluation, mitigating and presentation of possible
conse@uences on the environment of proposed actions at a
stage in decision ma"ing process so that environmental
damage can be minimi!ed or avoided.

'.3.1 WHAT EIA DOES

^ 7escribes the pro5ect or operation

^ 7escribes the environment that will be aJected

^ Predicts the impact on the environment

^ <dopts options, techni@ues and controls to reduce negative


impact.

^ ?onitors the pro5ect or operation to ensure that identi8ed


"ey impact is minimi!ed.

'.3.2 GOAL

^ To ensure that decision ma"ers consider the ensuing


environmental impacts when deciding whether to proceed with
a pro5ect or not.
 

11(

'.3.3 BENEFITS OF ENVIRONMENTAL IMPACT


ASSESSMENT

^ ?ay be prere@uisite for permit approval by government or


international agencies.

^ e@uired by 8nanciers of the proposed pro5ects

^ :elp to prevent environmental problem, ris" or costlytime


wor"ing liabilities.

^ Doosts Proponent &ompanys image.

^ epose con8dent assurance in Proponent &ompany.

'.3.4 ENVIRONMENTAL IMPACT ASSESMENT :EIA; OF A


NITRIC ACID PLANT.

• N)78) *7
 The ma5or negative impact of a nitric acid plant is ;O* emissions
of the tail gas from the absorption tower especially during start up
and shut down before the plant stabili!es. Others includeE

 is" of 8ree*plosion ha!ard.


 educed soil and marine water @uality.
 6ncrease in water and electricity demand.
  ;oise pollution.

  P+!78) *7
 Provide s"illed and uns"illed 5ob opportunities.
 ?a"e available nitric acid in the country, thereby encouraging the
production of fertili!er as it is a ma5or chemical used in its
production.
 

11>

 Dring development to the area where the plant is sited.


'.3.# NO EMISSION FROM NITRIC ACID PRODUCTION.

;itric acid production is one of the larger chemical industry


sources of ;O. =nli"e ;O* found in combustion -ue gas, ;O* from
nitric acid production is part of the process stream and is
recoverable with some economic value. Uent gas containing ;O*
is released to the atmosphere when the gas becomes too impure
to recycle or too low in concentration for recovery to be
economically practical.

 The chemical reactions for each of the nitric acid production


process steps demonstrate that ;O* must 8rst be created before
nitric acid can be produced. The 8rst reaction,


4;:# N $O2 4;O N 3:2O N heat

/@. 1

'hows ;O forming from the reaction of ;: and air. The ;O is then


o*idi!ed in the second step,


2;O N O2  2;O2 N heat

/@. 2

Producing ;O2. The ;O2  is subse@uently absorbed in water to


produce nitric acid. :owever, as the absorption reaction,


#;O2AgC N :2OAlC 2:;O# Aa@C N ;OAgC N heat,

/@. #
 

120

'hows, one mole of ;O is produced for every three moles of 


;O2absorbed, ma"ing complete absorption of the ;O* impossible.
 The unabsorbed ;O*, if not controlled, is emitted in the absorber
tail gas.

'.3.% FACTORS AFFECTING NO EMISSION LEVELS.


• eo*idation of ;O into ;O2 is a very slow reaction. <s more
air is added, the reaction becomes increasingly slower as the
reactants become diluted with e*cess nitrogen.
• 6ncreased temperatures due to e*othermic absorption tend
to reverses e@. # producing more ;O2.
• 9ow temperature Aless than #(0& _1000)`C is a "ey factor
forhigh absorption eciency but is also one that is dicult
and e*pensive to control.
• &ompletion of the absorption process which reduces ;O*
emission is aided by increased pressure A(00 to 1,400 "PaC
• 6ncreasing acid strength beyond design speci8cation
typically increases the ;O* emission rate.
• Hood maintenance practices and careful control ofoperations
play important roles in reducing emissions of ;O*.

'.3.& CONTROL TECHNIUES FOR NO EMISSIONS


FROM NITRIC ACID PRODUCTION .

  E7)6)6 ?!+-7+
/*tended absorption reduces ;O emissions by increasing
absorption eciency and is achieved by either installing a single
 

121

large tower, e*tending the height of an e*isting absorption tower,


or by adding a second tower in series with the e*isting tower.
6ncreasing the volume and the number of trays in the absorber
results in more;O* being recovered as nitric acid A11.$ more
acidC and reduced emission levels.

  N+$!))78) 77 -)6=7+ :NSCR;.


;onselective catalytic reduction uses a fuel and a catalystto

1. &onsume free o*ygen in the absorber tail gas.


2. &onvert ;O2 to ;O for decolori!ing the tail gas.
#. educe ;O to elemental nitrogen.

 The process is called nonselective because the fuel 8rst depletes


all the o*ygen present in the tail gas and then removes the ;O*.
6t can be operated at any temperature, heat used to operate it
can be recovered and it can achieve higher ;O* reduction than
e*tended absorption but it is e*pensive due to the cost of fuel.

  S))78) 77 -)6=7+ :SCR;


'elective catalytic reduction uses a catalyst and ammonia in the
presence of o*ygen to reduce ;O* to elemental nitrogen. The
process is called selective because the ammonia preferentially
reacts with ;O* in the absorber tail gas. The following sections
discuss '& used as a ;O control techni@ue for nitric acid plants.
Proper operation of the process re@uires close control of the tail
gas temperature.

  C/)6 A?!+-7+.
 

122

&hilled absorption provides additional cooling to the absorption


tower. This process is fre@uently used in addition to other control
techni@ues such as e*tended absorption. The principal advantage
of chilled absorption is improved absorber eciency due to lower
absorption temperature. :owever, chilled absorption by itself 
typically cannot reduce ;O* emissions to the level that any of the
three primary control techni@ues can achieve.

'.3.' ENVIRONMENTAL MANAGEMENT PLANT

 The following are actions ta"en to mitigate the negative impacts


of the plant sited above.

1. =se e*tended e*pander and chilled absorption to increase


absorber eciency and thus reduce ;O* emission.
2. 'ite the plant far away from residential area so as to reduce
noise pollution eJect and ris" of 8re.
#. =pdate on site emergency response plan.
4. :ave a generator to provide the electrical needs of the plant
and own water supply system.
$. ?onitor stac" gas emissions.
3. Test li@uid waste to ma"e sure the level of chemical in it is
acceptable before discharging to sea.
 

12#

CHAPTER (
ECONOMIC ANALYSIS

(.1 OVERVIEW

&hemical processes have been harnessed to transform resources,


and raw materials into more useful and hence more valuable
products to improve the living standards of people. This principle
is at the core of chemical engineering, and there industries have
matured over the last 100 years, and have been very successful
at creating wealth. The means of establishing which products to
ma"e and how to optimi!e the process re@uired for the
manufacture have been based on economic principles.
<pproaches to accounting for the ris"s to the economic value of 
pro5ects are also considered to ensure that they deliver the
e*pected bene8ts.

(.2 ECONOMIC CONSIDERATION

 The following are considered under economic evaluationF

1. C+!7 6 A!!)7! A+=75  This provides a survey of 


accounting procedures for the analysis of cost and pro8ts as
used for industrial applications.
2. C+!7 E!7*7+5  This provides information regarding the
estimation of 8*ed capital cost and also recurrent operating
e*penditure.
 

124

#. I7)-)!7 6 I8)!7*)7 +!7!5  This discusses the


concept and calculation of interest, i.e payment as
compensation for the use of borrowed capital.
4. T)! 6 I!=-)5  Ta*es represent a signi8cant
payment from a companys earnings and although insurance
rates are only a small fraction of annual e*penditure cover
for a plant is essential.
$. D)-)7+5 This is the measure of the decrease in value
of an item, with respect to time and can be considered as a
cost incurred for the use of the e@uipment.
3. P-+7?7, A7)-78)!, I8)!7*)7! 6
R))*)7!5  The pro8tability of an investment is a
measure of the amount of pro8t generated. 6t is important to
assess the pro8tability accurately and also the pro8t that
could be obtained from alternative investments.

10.4 TYPES OF COST

X.4.1 INDIRECT COST


1. D)! 6 )))- +!7  which cover the cost of 
design and the cost of Sengineering the plantE purchasing,
procurement and construction supervision. Typically 20 to
#0 of the direct capital cost.
2. C+7-7+-! ))!5  if a contractor is employed his fees
Apro8tC would be added to the total capital cost and would
range from $ to 10 of the direct cost
#. C+7) +)5 this is an allowance built into the
capital cost estimate to cover for unforeseen circumstances
 

12$

Alabor disputes, design errors, adverse weatherC typically $


to 10 of the direct cost.

 Table >.1E typical factors for estimation of pro5ect 8*ed capital


cost

?<VO /\=6P?/;T , TOT<F P&/


P=&:<'/ &O'T A)1 TO )>C
/@uipment erection 0.40
Piping 0.+0
6nstrumentation 0.20
/lectrical 0.10
Duilding process 0.1$
=tilities 0.$0
'torage 0.1$
'ite development 0.0$
<ncillary buildings 0.1$

(.4.2 T+7 /! 7 +!7 :PPC;

PP& [ P&/ A1 N  factors C [ P&/  #.4

anging from f10 to f12

7esign and engineering 0.#0


&ontractors fee 0.0$
contingency 0.10
)i*ed capital [ PP& A1 N f10 N f11 N f12C [ PP&  1.4$
 

123

(.4.3 OPERATION COSTS

<n estimate of the operating costs, the cost of producing the


product, is needed to 5udge the viability of a pro5ect and to ma"e
choices between possible alternative processing schemes. These
costs can be estimated from the -ow sheet, which gives the raw
material and service re@uirements, and the capital cost estimate

 The cost of producing a chemical product will include the items


listed below. They are divided into two groups.

1. F)6 7 +!75 &osts that do not vary with production


rate. These are the bills that have to be paid whatever the
@uantity produced
2. V-?) +)-7 +!75 &osts that are dependent on the
amount of product produced.

(.4.4 FIXED COSTS


1. ?aintenance Alabor and materialsC
2. Operation labor
#. 9aboratory costs
4. 'upervision
$. Plant overhead
3. &apital charges

(.# COST ESTIMATION

(.#.1 THE RATIO METHOD


 

12+

 The ratio method is a simple techni@ue whereby "nown capital


cost data for an e*isting chemical plant are ad5usted to provide a
cost estimate for the desired plant capacity. This method is also
able to update 8gures to account for in-ationary eJects of past
years. )inally the capital cost 8gure is ad5usted for e*change rate
diJerences between countries .The method is centered around
the use of "ey cost estimation indices such as the &/ plant cost
inde* and the ?arshall and 'tevens A?W'Cinde*.

R7+ *)7/+6 =7+!


n
capacity of designed
Cost of Designe pl!nt   ¿ Cost of previous plant ( Capacity of previous plant )

0.6
  1200 tons 1200
Cost of    =Costof  280 tons / day (  )
day 280

cost of   280 tons /day =¿ ! 60 "illion

 ThereforeF

0.6
1200
cost of   1200 / day = ! 60 "illion (  ) [ 14#.33 million
280

[ 22.+ billion

(.#.2 STEP COUNTING METHOD

'tep counting estimating methods provide a way of ma"ing a


@uic" order of magnitude estimate, of the capital cost of a
proposed pro5ect. The techni@ue is based on the premise that
the capital cost is determined by a number of signi8cant
 

12(

processing steps in the overall process. )actors are usually


included to allow for the capacity, and comple*ity of the
processE material of construction, yield, operating pressure and
temperature.

• !7) +=7 *)7/+6 =7+!F


0.615
C =14000 NQ

Khere \[plant capacity, tonne per year.

;[number of functional units

&[capital cost.

\[400,000tonsyr

;[1#

0.615
C =14000  13 ( 400,000 )

[ ! 507 "illionequivalent ¿ 79.8 #illion naira .

 (.#.3 FACTORIAL METHOD

&apital cost estimates for chemical process plants, are often


based on an estimate of the purchase cost of the ma5or
e@uipment items, re@uired for the process, the other costs being
estimated as the factors of the e@uipment cost .The accuracy of 
this type of estimate will depend on which stage the design has
reached at the time.
 

12>

ECONOMIC ANALYSIS CALCULATIONS

ESTIMATION OF FIXED CAPITAL COST

  R+=/ E!7*7)
&f  [ )l &e

&e [ ₦ (24.4# million

&f [ 4.+  (2(.4# [ ₦ #.(> billion

• D)7)6 E!7*7)

PP& [ &e A 1 N factors C

factors [ #.#

PP& [ (24.4# A1 N #.#C [ ₦#.$$ billion

 Total )i*ed &apital [ #.$$ A 1 N 0.4$C [ ₦ $.1$ billion

Kor"ing capital [ $  $.1$ [ ₦2$( million

 Total &apital 6nvestment &ost [ Total )i*ed &apital N Kor"ing


&apital

 Total &apital 6nvestment &ost [ $.1$ N 0.2$( [ ₦$.41billion

OPERATING COST ESTIMATION

V-?) C+!7  ₦ *+

1C aw materials 0.2$


 

1#0

2C ?iscellaneous 0.24

#C =tilities &ost

&ooling water ;egligible

'team ;egligible

Power 0.4

4C 'hipping  Pac"aging 1.1$

  T+7 2.04

FIXED COST

   ₦ M+

1C ?aintenance 1.21
2C Operating 9abor +.23
#C 9aboratory &ost 2.1(
4C Plant Overhead #.3#
$C 6nsurance #(+.1$
3C oyalties ;ot applicable
T+7 401.4#

<nnual Total Operating &ost [ 2.04 N 401.4# [ ₦ 40#.4+


million
<nnual Operating &ost ounded [ ₦ 40#.$ million

ANNUAL PROFIT CALCULATION

 Total /*penses [ operating cost N capital 8nance cost


 

1#1

 Total 8*ed capital investment [ ₦$.1$ billion

Kor"ing capital [ ₦ 2$( million

 Total capital cost [ ₦ $.41 billion

A<ssuming $ compound interest rate annually and 2 years


investmentC

 Total interest [ p A1 N r Cn

  [ $.41 A1 N 0.0$C2

 
[ ₦ $.>3 billion

Operating cost for 2 years [ 2  0.40# [ ₦ (03 million

 Total /*penses [ ₦ A0.(03 N $.>3C billion

  [ ₦ 3.++ billion

  &ost of ;itric acid per ton [ ₦10$00

  <nnual total cost of ;itric acid [ +100  400,000

  [ ₦4.2 billion

 Total cost of Product for 2 years [ ₦(.4 billion

<nnual total cost of steam [

10$00 "g (000 hours   ₦ +.$


hour 1 year 4$4"g
 

1#2

<nnual total cost of steam [ ₦ 1.#> million

 Total income before ta* [ ₦ A$.3( billion N 2  0.001#> billionC

  [ ₦ (.4 billion

 Total income after ta* Abased on 2.$ ta*C [ ₦ A(.4  0.02$  (.4C
billion

[ ₦ (.1> billion

Pro8t after ta* [ ₦ A(.1> 3.++C billion [ ₦1.42 billion

Paybac" period Ano interestC [ 7epreciable )&6  Total pro8t

  [ $.1$  1.42 [ #.3# years

 Therefore, paybac" period [ 3)-! ' *+7/! -+=6)6.

BREAK EVEN ANALYSIS

On the assumption that mar"et price of nitric acid will remain


constant for a reasonable length of time. The brea"down period
for the plant will simply be the inverse of the rate return on the
investment

$otal capitalinvest"ent 

 Drea" even time AyrsC [ annual net profit 

5.41
¿ =3.81 yrs
1.42

Drea" even time[ 3-! 10 *+7/!.


 

1##

RATE OF RETURN ON INVESTMENT

 O  [ yearly pro8t  total initial investment  100

  [ 1.42$.41  1001 [ 2%.2#J

CHAPTER TEN
 

1#4

STARTUP AND SHUTDOWN PROCEDURES

  'hutdown is that period of time during which a boiler, gas


turbine, process heater or nitric acid production unit is allowed to
cool from its normal temperature range to a cold or ambient
temperature.

 The shutdown philosophy is based on the nitric acid plant process


control and safeguarding philosophy reference and adapted to
suit the developments in the design. :igh nitric acid supply
availability is of paramount importance. The level of safeguarding
re-ects the need for the plant to operate safely whilst ensuring
ma*imum availability.

  'hutdowns of the main process will be avoided as much as


possible within the constraints of safer operation. <dditional time
is given to the operator to correct process upsets by intentionally
accepting cascading events. This in turn will result in fewer
disruptions in the process

)or all separators, low low li@uid level will cause the
corresponding li@uid outlet '7U A'hut down UalvesC to close rather
than generating an O'7 AOperational 'hut 7ownC

• On high li@uid level and high pressure in the main nitrous


gas stream, gas -ow is stopped by closing the inlet
shutdown valves. This is to avoid li@uid carry over to the
absorption column and stripper.
• Has compressor unit.
 

1#$

• 6n the absorption column, a high li@uid level and a high


pressure will close the corresponding inlet 'OU.
•  Trips in the oJ air compressor pac"age will stop the
compressor and the air -ow will be directed to the -are.

10.1 EMERGENCY SHUTDOWN :ESD; AND


EMERGENCY DEPRESSURI@ATION :EDP;

/mergency 'hutdown and 7epressuri!ation of pressuri!ed vessels


and piping is the ac"nowledged way to reduce the li"elihood of 
escalation from accidental hydrocarbon release incidents.

<n /'7 will be automatically initiated on con8rmed low


instrument air pressure and manually initiated on con8rmed gas
detection via /'7 push button. The aim of an /'7 is to bring the
plant to a safe condition byF

1. 6solate the plant from the -ow lines, stopping all


hydrocarbons containing streams from coming in and going
out of the plant.
2. 7epressuri!ation the plant.
#. 'tarting down the 8red heaters

10.2 NOTIFICATION
Prior noti8cation of scheduled shutdowns and scheduled startups
following scheduled shutdowns shall be made in a timely manner
and form. 'hutdowns and startups must be scheduled in pairs
with scheduled dates for each. ;oti8cation of scheduled startups
and shutdowns is re@uired only if an e*emption from the
 

1#3

emissions limit is re@uired. This noti8cation shall contain the


following informationE
1. 7ates and times of the scheduled startup and shutdown and
its duration, and
2. <ny other process variable that is appropriate as
determined.

10.3 RECORD KEEPING


ecords shall be maintained and "ept onsite and made available
for two years indicating hourbyhour 8ring rates, -ue gas
temperatures, ;O* emissions and such process variables that are
appropriate.
Once all of these e@uipment chec"s are performed, the complete
unit is disassembled, all parts and bearings are rechec"ed and
oiled, the lubrication system is drained and -ushed, and the train
is reassembled. < timeconsuming aspect of the drive train
chec"out involves plotting of the units surge curves. Once the
unit is operational, the air compressor can be used to blow out
downstream air and stream lines.

Other e@uipment debugging procedures are performed according


to individual Spunch lists and are summari!ed as followsE

• L=6  6 +6)6 8)!!)!E Pressure tested with


water at ma*imum wor"ing pressure.
• G! )!5 cannot be chec"ed until plant is operating
• R)) 88)!E bench tested with re@uired pressureif 
serious problems e*ist, they are sent out for repairs.
 

1#+

•H)7 )/)-5 -ushed with water or a cleaning solution.


• W!7) H)7 B+)-E undergoes a hydrostatic chec" followed
by pretreatment with chemicals to prevent corrosion due to
o*ygen or water prior to plant startup. < 8nal procedure before
production starts consists of 8lling the boiler with water and
warming with steam to prevent shoc" to the system
• A?!+-?)- +=*E shipped to the plant as a complete
pac"age and can be of either a bubble cap or sieve tray
arrangement. The column is prepared by -ushing with water to
clean and chec" -ow and level indicating instruments. 'ieve
tray columns are more sensitive to gas versus li@uid -ow and
may re@uire 1hr to seal properly whereas a bubble cap unit
may ta"e about 20mins
• I!7-=*)77+5  &annot be installed until all other
e@uipment is in place. < critical component is ammoniaair ratio
control system which must be accurately calibrated to read
concentrations of about >11 Percent ammonia in air.
10.4 STARTUP OPERATIONS

Once all e@uipment is installed and thoroughly chec"ed for proper


mechanical operation Athis may ta"e from 2 to 3 monthsC, the
plant is ready to undergo initiation of nitric acid production.
Preliminary startup operations consist of the following stepsE

1. 'tartup of air compressor system

2. 6nitiation of water -ow to absorber tower


 

1#(

#. Platinum gau!e lit by hydrogen torch to initiate burning of 


ammonia A-ame is selfsustainingC
4. <mmonia -ow is begun
  Kithin 2 to # wee"s of this initial startup, the plant is ready for a
test or demonstration run. Test runs usually last #, +, or 14 days
depending on the contract. 7uring this time, the plant must
achieve its pea" eciency, of ma*imum design rate, and meet all
applicable emission regulations. < violation of any of these
conditions or other e@uipment malfunctions results in a cessation
of the test run. The conclusion of a successful test run results in
the Slegal acceptance of the plant from the contractor.

 The best point in time to de8ne plant startup is when the


ammonia -ows to the converter is initiated. Darring no usual
problems, the completion of a successful test run and the
achievement of ma*imum production rate should be about one
month or less from this starting point. <n important point with
respect to nitric acid facilities is that the summer months are the
most critical for proper operation due to cooling re@uirements for
the e*othermic reaction involved. )or this reason, most new
plants try to come online during the hotter periods when a
successful test run would be most meaningful. Decause of the
re@uirement for performance testing within 1(0 days of startup, it
is conceivable that testing could be re@uired during the cooler
months when a plant would 8nd it easiest to meet applicable
emission limitations. 6n this instance, regulatory agencies might
want to conduct testing as soon after startup as possible, consider
 

1#>

postponement of tests until the following summer, or consider


winter testing and subse@uent summer testing.

CHAPTER 11
CONCLUSION AND RECOMMENDATION
11.1 CONCLUSION
)rom the design procedures followed and results obtained, it can
be concluded that a plant can be set up to produce 400,000
tonnes of ;itric acid per annum from ammonia o*idation. The
e*cess steam generated in the process can be gathered and sold
to increase the total income to be reali!ed from sale of products.
<lso, the e*haust gases from the turbine is reduced to the lowest
minimum AQ1000ppmC. This is to reduce the ;O* emission from
the plant which is in line with the )ederal /nvironmental
Protection <gency A)/P<C regulations. The produced acid will be
sold mainly to fertili!er manufacturing plants and oil servicing
companies in ;igeria, and can be e*ported as well.
)inally, an economic evaluation of the plant showed that the rate
of return on investment is about 23.2$ and the paybac" time is
about #years and + months. Therefore the pro5ect can be said to
be economically feasible.
 

140

11.2 RECOMMENDATION
<dditional control schemes should be put in place to ensure very
low nitrous o*ide emissionF this will contribute to the global
ob5ective in reducing environmental degradation. There should be
considerations for a two stage air compression to supplement the
-uctuations in air re@uirement due to the anticipated increase in
the demand of nitric acid. There should be provisions for
preventive maintenance, as this will help to reduce fre@uent
shutdowns due to repairs. 6t is also anticipated that this plant will
be part of a larger chemical comple*. <mmonia will be produced
by steam reforming of natural gas. The nitric acid plant will ta"e a
portion of the ammonia product, and nitric acid and ammonia will
then be used to produce ammonium nitrate.
 

141

REFERENCES
<babio, O.Y. 200$, ;ew Heneral &hemistry, <fricana )ep
Publishers, 'ydney.

<ne"e, 9. /. 200>,   Principles of chemical engineering process


design,

7eadroit innovation, /nugu.


 

<non, <. 1>+> I;itric <cid rolls on &hemical /ngineering 2>
 Vune, pp. 242$.

Doland, 7. W 9innhoJ, D. 1>+> IThe preliminary design of


networ"s for heat e*changers by systematic methods
&hemical /ngineering, 9ondon 22 <pril, pp. 2$2+.

Drown, G. V. 1>(> Process integration initiative Areview of the


process integration initiatives funded under the /nergy
/ciency W7 ProgramC, /nergy Technology 'upport =nit,
:arwell 9aboratory, 7idcot =nited Gingdom, pp. 2212#3.
 

142

&anon, D.K 1>>( 'afety and health in wor"place, ;ostrand


ein hold, ;ew Yor", pp.20120#.

&heremisinoJ, ;. P. 2000, &hemical process e@uipment,


Dutterworth :eineman, ;ew 7elhi.

&hilton T.:. IThe manufacture of nitric acid by o*idation of


<mmonia E the 7u pont pressure process &hemical /ngineering
Progress, ?onograph 'eries Uol. $3, <6&he, ;ew Yor".

&oulson V. ?. W ichardson V. ). 2004  &oulson W ichardsons


&hemical engineering, 3th /d. Uol. 1, /lseiver publishers
9ondon.

7urilla, ?. 200>, ;O* and ;O 2 control in nitric acid plants,


\ueens Publishing :ouse, =.'.<.

)elder . W ousseau . 2000,  /lementary principles of


chemical processes, #rd /d. Vohn Kiley W sons, ;ew Yor".

Hregory T.& 1>>>, =ses and <pplications of chemicals and


related materials, einhold Publishing, ;ew Yor".

:arvin .9, 9eray 7.H W oudier 9. 1>+>, I'ingle pressure or


dual pressure nitric acidE an ob5ective comparison, <mmonia
Plant 'afety, Uol. 21, pp.1+#1(#, <6&he, ;ew Yor".
 

14#

:immelblau, 7. ?. 200#, Dasic principles and calculations in


chemical engineering, 3th /d. Prentice :all, 6ndia.

:ouse, ). ). 1>3> I/ngineers guide to plant layout &hemical


 
/ngineering, "# +3 Vuly 2( p.120.

Gent V.<, 1>(#, eigels :andboo" of 6ndustrial &hemistry, Uan


;ostrand anhold Publishing, ;ew Yor".

Gir" D./ W Othmer 7.) A/dsC 1>(1, /ncyclopedia of &hemical


 Technology #rd /d. Uol.1$ Kiley6nterscience, ;ew Yor", pp.($#
(+1.

9innhoJ, D, 7unford, : W 'mith,  1>(#, :eat integration of


distillation columns into overall processes, &hem. /ng. 'c.,
#(A(C, pp. 11+$11((.

?artyn, '.. W 7avid, K. V. 1>(>, &hemical engineering designE


a case study approach, Dell and Dain 9td, Hlasgow.

?a*, '.P, Glus, 7. T. W onald, /.K 200#, Plant design and


economics for chemical engineersF $th /d., ?cHraw:ill, ;ew
 Yor".

Ohrue T., Oh"ubo G. W 6mai O. 1>>>, Technological


improvements in strong nitric acid process, Uol. 21 pp.1341+0,
<6&he, ;ew Yor".
 

144

Perry . :., Hreen 7. K. W ?aloney V. O 200(, Perrys &hemical


/ngineers :andboo", (th /d. ?cHraw:ill, ;ew Yor".

'innot, .G 200$, &hemical engineering design, 4th /d.,


Dutterworth:einemann, 9ondon.
 

14$

APPENDIX I

TABLES AND CHARTS

 Table <.1E &onversion factors for some common '6 units


 

143

 Table <.2E Typical Overall &oecient


 

14+

 Table <.#E Typical 7esign stress for Plates


 

14(

)igure <.1E Temperature correction factorE for one 'hellF two or


more even tube passes :eat e*change

<PP/;76R 66
MATERIAL BALANCE CALCULATION

$!sis: 1hour 

4000000tons :;O# 1 year


1 year (000 hours
  [$0tons:;O#
solutionshour
 

14>

ABSORBER AND STRIPPER


#;O2N:2O 2:;O#N;O

$0tons :;O# solution 0.3 tons :;O#


1 ton :;O# solution

 
[#0 tons :;O# Produced

#0 tons # tons 1 ton mole 43 tons ;O2 100 tons


:;O# moles ;O2 :;O# ;O2 fed
2 ton moles   3# tons 1 ton mole >( tons ;O2
:;O# :;O#  ;O2 converted

[##.$2( tons ;O2 fed

1 ton mole ;O #0 tons:;O# 1 ton mole #0 tons ;O


:;O#
2 ton moles 3# tons :;O#  1 ton mole ;O
:;O#
  [ +.14# tons ;O Produced

OXIDISING UNIT


2;ONO2 2;O2

##.$2( tons  1 ton mole O2 1 ton mole ;O2 #2 tons O2


;O2 fed
2 ton moles 43 tons ;O2 1 ton mole O 2
;O2
 

1$0

 [11.332 tons O2 converted

11.332 tons O2 1 ton mole O2  2 tons moles  #0 tons ;O


;O
#2 tons O2  1 ton mole O2 1 ton mole ;O
  [21.(33 tons ;O converted

11.332 tons O2 1 ton mole O 2 2 tons moles   #0 tons ;O


;O fed fed
#2 tons O2  1 ton mole O2 1 ton mole ;O
fed fed
 [21.(33 tons ;O fed

CONVERTER


4;:#N$O2 4;ON3:2O

2#.1>+ tons $ tons moles 1 ton mole ;O #2 tons O2


;O O2 converted converted
4 tons moles  #0 tons ;O 1 ton mole O2
;O converted
[#0.>2> tons O 2 converted

\uantity of O2 fed to the converted[ A11.332N#0.>2>C [42.$>1


tons O2 fed.

2#.1>+ tons 4 tons moles 1 ton mole ;O 1+ tons ;:#


;O ;:#
4 tons moles #0 tons ;O 1 ton mole
;O ;:#
 [1#.14$ tons ;:# converted.
 

1$1

1#.14$ tons ;:# 1 ton ;:# fed


0.>( ton ;:# converted
 [1#.41# tons ;:# fed.

\uantity of ;:# leaving converter[ A1#.41#1#.14$C [0.23( tons


;:#.

2#.1>+ tons   3 tons moles 1 ton mole ;O 1( tons :2O


;O :2O
  4 tons moles #0 tons ;O 1 ton mole :2O
;O
 [20.(++ tons :2O Produced.

0.00$ tons :2O 1#.41# tons ;:#


0.>>$ tons ;:#
 0.03+>

 Total \uantity of :2O leaving &onverter[ A20.(++N0.03+>C [


20.>$ tons.

?a"e up :2O is added to ensure ecient chemosorption.

\uantity of ma"eup water[ +.0$>

\uantity of :2O fed to <bsorber[ A+.0$>N21.$(2C [ 2(.341 tons


of :2O.

#0 tons :;O# 1 ton mole 1 ton mole : 2O 1( tons :2O


:;O#
3# tons :;O# 2 tons moles 1 ton mole : 2O
:;O#
  [4.2(3 tons :2O e@uired.

[0.34 tons O2
 

1$2

O2 left to react[3.#2 tons O2 3.>3  0.34

<ssume $0 conversion of ;O

<mount of ;O reacted [ 0.$  (.3 [4.#tons ;O

0.2+ tons ;:# $ mols O 2   1 mol ;:# #2 tons O2


4 mols ;:# 1+ tons ;:#   1 mol ;:#

4.# tons ;O 1 mol O2  1 mol ;O #2 tons O2


2 mol ;O #0 tons ;O 1 mol O 2

[2.2>tons O2 reacted

<mount of leaving stripperE 3.#2  2.2> [ 4.0# tons O 2

<mount of ;O left unreactedE (.3  4.# [ 4.# tons

[0.4( tons ;O

 Total amount of ;O leaving stripper [ 4.# N 0.4( [4.+( tons ;O

0.2+ton ;:# 3 mols :2O 1 mol ;:# 1( tons :2O


4 mols ;:# 1+ tons ;:#   1 mol :2O
 

1$#

0.43 7+! H2O


T+7 *+=7 + 7)- 8+- )8 7/) !7-)-  23.'3
 0.43 $20 4.2% 7+!
NB5 A*+=7 +H2O  HNO3 !+=7+ 20 7+!.

4.3 7+! NO 2 *+! NO2 1 *+ NO 4% 7+! NO2


2 *+! NO 30 7+! NO 1 *+ NO2
%.#( 7+! NO2
T+7 NO2  )8 !7-)- %.#(  0.%&2  &.2%2 7+!
NO2

COMBUSTION CHAMBER AND PURIFICATION REACTOR.


COMBUSTION CHAMBER
CH4  2O2 CO2  2H2O
2C2H%  &O2 4CO2  %H2O
2H2  O2 2H2O
2NO  O2 2NO2
A!!=*) 10 7+)! + 7=- ! !=)6 7+ +*?=!7+
/*?)- 7/ +*+!7+  7 J
CH45'#.&, C2H%5 4.', N25 3.2, H25 %.3
'.&# 7+! CH4 2 *+! O2   1 *+ CH4 32 7+! O2
1 *+ CH4 1% 7+! CH4   1 *+ O2
34.2' 7+! O2 -)=-)6
'.#& 7+! CH4 1 *+ CO2   1 *+ CH4 44 7+! CO2
1.02 1 *+ CH4 1% 7+! CH4   1 *+ CO2
23.10 7+! CO2
'.#& 7+! CH4 2 *+! H2O 1 *+ CH4 1' 7+! H2O
1.02 1 *+ CH4 1% 7+! CH4   1 *+ H2O
 

1$4

1'.( 7+! H2O

0.4' 7+! & *+! O2   1 *+ C2H% 32 7+! 02


C2H%
2 *+! C2H% 30 7+! C2H%   1 *+ O2
1&.(2 7+! O2
0.4' 7+! 4 *+! CO2   1 *+ C2H% 44 7+! CO2
C2H%
1.02 2 *+! C2H% 30 7+! C2H%   1 *+ CO2
1.3' 7+! CO2
0.4' 7+! % *+! H2O 1 *+ C2H% 1' 7+! H2O
C2H%
1.02 2 *+! C2H% 30 7+! C2H%   1 *+ H2O
0.'4& 7+! H2O
0.3 7+! H2 2 *+! H2O 1 *+ H2 1' 7+! H2O
2 *+ H2 2 7+! H2   1 *+ H2O
2.& 7+! H2O
N>B5 A!!=*) #0J +8)-!+ + H 2, (0J +8)-!+ + 
CH4 6 C2H%,30J +8)-!+ + NO
A*+=7 + CH4 )8 +*?=!7+ /*?)-  '.#&:0.1;
 0.'#& 7+!
A*+=7 + C2H% )8 +*?=!7+ /*?)-  0.4':0.1;
0.04' 7+!

APPENDIX III
ENERGY BALANCE CALCULATION
U7 35 THE COMPRESSOR
 
T 20C T+=71##C
 

1$$

$  2

H)7,   H  ∫ Cpd$ 


$  1

C+*+)7! 8+8)6 N2  O2


S) /)7 7)!
N2  1.04 K">KK 6 O2  0.%4'% K">KK 
E7/, H

H1 1.04:42'   −293 ;  140.4 K">K

H2  0.%4''%:42' 2(3;  '&.#%K">K


H3  0.%4'% :42' Q 2(3;  '&. #%K">K

 H)7 +=7=7 -+* 7/) C+*-)!!+-


  H   HO=7  HI
1'&030:140.4;  4(&20 :'&.#%; 4(&20 :'&.#%;
  2%2#(01 K">/-
L)7   V+=*)7- +-7) + -
  F->> D-
F-  F+ -7) + -, D-  D)!7 + -
  23%&#0 K>*3>1.1&'K>*3  200(&%.23 *3>/-
T/)+-)7 P+)- + 7/) C+*-)!!+- P11 :P1 >P2;
 1 200(&%.23  :&.3> 1;  3((#1#.4( K">/-
$heoretical po%er
A7= S/7 W+-< -)=-)6   &fficiency

 3((#1#.4(> 0.'4  4&#%13.%'K"

U7 #5 AIR HEATER


 

1$3

T  1##C T 0=7  2#0C


E7/, H
533

H1 6 H3  ∫ 0.9454+1.315  10 $4
T  −5897.46 T$2
428


1#2.4'4K">K

H2  0.(&3#04T  1.&%  10 $4
T2 11'&.2T$1

'0.&( K">K

H)7 D=7 + 7/) A- H)7)-,    ' H   HO=7   HI

  1'&030:'0.&&'2;  4(&20:1#2.4'4; Q 4(&20:1#2.4'4;


 1#10&(4%.&# K">/-
U7 ' THE CONVETER

R)7+! 8+8)6  7/) C+8)-7)-


4NH3  #O2 4NO  %H2 H-  (0& K">K 
B) 7/ -)7+
  H  H-  O=7 HO=7 H
  )7)7 + -)7+
 :2&0  13#00;> $4  330&.#0 K">/-
S) H)7 7 + NH3

C>R : 3.#&'  3.020  10 $3


T  :$0.1'%    10 #
T$2;; 

0.4''

C=7 7/) )7/)!


H1 6 H#  1.0142:11%3 #23;  %1#.#' K">K
H2 6 H&  1.0'3' :11%3 Q #23;  %(3.%32 K">K
 

1$+

1163

H4    ∫ 1.7461 +1.47376  10


523
$3
T Q (0&%.'T2


303#.0( Q 1132.10  1(02.(( K"> K
1163

H%  ∫ 0.9385 +0.173  10 $4
T  3'&.(4T$2;
523

 %10.3' K" >K


H)7 +=7)7,   330&.#:$(0&.3;  :2&0

427 ( 612.58 )+160860 ( 693.632)+ 65 ( 1305.98 )


 1902.99 + 1160 ( 612.58 ) + 21060 ( 1305.98 ) ( ¿

  20#&(2&3.'# K">/-
U7 ( WASTE HEAT BOILER

I)7 T)*)-7=-)  '(0 ) C 6 O=7)7 T)*)-7=-)

2#0C
E7/)! + 7/) +*+!7+!

0.9454 + 1.315  10
¿
T   −5897.46 T$2;
523
$4
H1 6 H3 
∫¿
1163

 #23.&0 Q 11(3.#0  $%%(.' K">K

H2 6 H4  $&1(.2# K">K

H#  $%'#.0'' K"> K

 :11%0 :$%%(.';  1%0'0: $&1(.2#;  23320:$%'#.0''; Q


11%0:$%%(.';  1%0'%0:$&1(.2#;
 

1$(

  $1#(&%2#2K">K

T)*)-7=-) + S7)* +* +=7 -+* 7/) W!7) H)7


B+)-

  *C :TST Q TCW;

* 1000K>/-

TCW30C, C  4.2 K">/-

TST $30  1#(&%2#2>1000  4.2  

TS7)*410C

 U7 135 STACK GAS HEATER


 

T  200C  TO=7 


1#0C

H1 6 H3  0.(&3#04T  '.'  10 $#


T2 −¿  11'&.2T

 $#2.(0( K">K

H2 6 H #  C ' T  1.31:$#0;  $%#.#K">K

H4 $#0.(0%K"><
  1%0'%0:$#2.(0(;  14%0:$#0.(0%;  33#30:$%#.#; Q
1%0'%0:$#2.(0(;  33#030:$%#.#;
 $&4322.&% K">K
¿
$&4322.&%  13#%#  2.15  ¿ TST $30;
 

1$>

TS7)* 11'.4'

U7 125 WASTE HEAT BOILER


I)7 T)*)-7=-)  1#0C  423K 
O=7)7 T)*)-7=-)  #0C  323K 
E7/)!, H

H1 6 H3  0.(&3#0T  '.'  10 $#


T Q 11'&.2T$1

 $102.#( K">K
H2 6 H#  131 K">K
  1%0'%0:$104.&34;  14%0:$102.#(;  33#30:$131;
$14(&'1.4 K">/-
TS7)*103C

AMMONIA VAPORI@ER
 ƛ 13#%#  2.1#:T 33.4;
ƛL7)7 /)7 + S7)* 1(10.3
14(&'1.4
T  1#1%(.14> :13#%#2.1#; $33.4 $2'.1((C
AMMONIA SUPERHEATER
 $1#(%2#2K">/-, ƛ3300

 ƛ  13#%#2.1#:T  2'.2;


T  :1#(%2#23300;> :13#%#2.1#; $2'.2
T2%.%#C
 

130

APPPENDIX IV
EUIPMENT DESIGN CALCULATION
STACK GAS HEATER

\ [ +4#22.+3GVh, Th in  [2000&, Th   [ 1$00&, Tc in [ #00&,Tc out


out

[11(.4(0&, = [0.102Gwm2

&onverting \ [ +4#22.+3GVh to GVs

+4#22.+3#300 [20.34$2GVh

$" =( $h ¿−$c out )−( $hout −$c ¿ )


$h¿ −$c out 
ln  [ ]
$hout −$c ¿

( 200 −118.48 )−( 150 −30 )


(200 −118.48 )
ln  [  ]
(150−30 )

81.52−120
 81.52
ln
120

38.48
0.387

o
' $ "=99.43 C 

Q
 + =
U ' $ "

20.6452
0.102  99.53

  < [ 2.0#m2
 

131

AMMONIA VAPORI@ER
149781.4 ,-  149781.4
Q=   . ∈ ,- / sec=   = 41.606 ,-  / /
hr 3600

o
$c ¿ =−33.4 C 

o
out =¿−28.199 C 
$c¿

$h¿ =208

( $h¿ −$cout )−($hout −$c¿ )
$hout =167.2 ' $ "=
$h¿− $c out 
ln  [ ]
$hout −$c ¿

( 208 +28.199 )−(167.2+ 33.4 )


 208 + 28.199
ln  [  ]
167.2+ 33.4

236.199 −200.6
236.199
ln  [  ]
200.6

35.599 35.599
=  =218. 4 o C 
ln1.177 0.163

= [ 0.102GKm 2
  Q   41.606
 + = = =1.868 "2
U '$" 0.102  218.4

WASTE HEAT BOILER 1


 

132

( $h¿ −$cout )−($hout −$c¿ )
' $ "=
$h¿ −$cout 
ln  [ ]
$hout −$c ¿

(890 −410 )−(250−30 ) 480 −220


=
890− 410  480
ln  [  ] ln
250 − 30 220

' $"=333.76

  Q   4437.8  4437.8
 + = = =  =130.73 "2
U '$" 0.102  333.76 34.04

WASTE HEAT BOILER 2


(208 −150 )−(50 −32 ) 58− 18   40
' $"= = = =34.48
208−150  58 ln3.2
ln  [  ] ln
50− 32 18

Q
 + =
U'$"

\ [ 14>+(1.4GVhr, converting to GVs

[ 41.31GV'
41.61 2
=11.83 "
0.102  34.48

NH3 SUPERHEATER.
 

13#

( $h¿ −$cout )−($hout −$c¿ )
' $ "=
$h¿ −$cout 
ln  [ ]
$hout −$c ¿

( 410−26.65 )−(330−28.2 )   81.55


' $"= = =340.9 5o C 
410 −26.65 ln 1.2702
ln  [  ]
330 −28.2

\ [ 44#+.($GV'.

= [ 0.102GKm 2
  4437.85 2
 + = =127.6 "
0.102  340.95

AIR HEATER

\ [ 14((14(3.+$GVhr [ 41##.+GV'.
(350 −250 )−(200 −155 ) 100 −45   55   55
' $"= = = = = 68.8 4 o C 
350− 250 100 ln 2.22 0.799
ln  [ ] ln  (  )
200 −155 45

  Q 4133.7
 + = =   =588.7 "2
U '$" 7.02
 

134

APPENDIX V

EUIPMENT COSTING CALCULATION

6; 1>>(
2 0.6
2 2   +"
Cost ∈ + " =cost of  500 " ( 2
)
500 "

6; 201#
2013 inde0
Cost ∈ 2013= cost ∈ 1998  (  )
1998 inde0

6nde* in 1>>( [ #>0

6nde* in 201# [ 3(#.3

AMMONIA VAPORI@ER
 

13$

&ost of $00m2 [ ;1.(4 million

< [ 1.(+m 2
0.6
1.87
Cost ∈ 1998= N 1.84 "illion (  ) = N  0.06 "illion
500

683.6
Cost ∈2013= N   0.06 "illion (  )
390

; 0.11 million.

WASTE HEAT BOILER 1

6; 1>>(
2 0.6
2 2  + "
Cost ∈ + " =cost of  500 " ( 2
)
500 "

6; 201#
2013 inde0
Cost ∈ 2013= cost ∈ 1998  (  )
1998 inde0

6nde* in 1>>( [ #>0

6nde* in 201# [ 3(#.3

&ost of $00m2 [ ;1.(4 million

WASTE HEATER BOILER 2

6n 1>>(
0.6
2 11.8
Cost ∈ + " = N 1.84 "illion (  )
500
 

133

0.6
 N 1.84 "illion ( 0.0236 )

2  N  1.84 "illion 0.106


cost of + " =
 N  0.19 "illion

6n 201#
683.6
cost of   2013= N  0.19 "illion   = N  0.33 "illion
390

AMMONIA SUPERHEATER

< [ 12(m2

&ost in 1>>(
0.6
2 128
Cost of   128 " = N  1.84 "illion( ) = N  0.8214 "illion
500

&ost in 201#
 683.6
cost of   2013= N  0.8124 "illion   = N   1.424 "illion
390

WASTE HEAT BOILER 1

< [ 1#0.$m 2

6n 1>>(
2 0.6
2 2   +"
Cost ∈ + " =cost of  500 " ( 2
)
500 "

0.6
2 130.5
Cost of   130.5 " = N   1.84 "illion(   ) = N   0.8219 "illion
500

 683.6
cost of   2013= N  0.8219 "illion   = N  1.44 "illion
390

FOR AIR HEATER


 

13+

6; 1>>(
2 0.6
2 2  + "
Cost ∈ + " =cost of  500 " ( 2
)
500 "

6; 201#
2013 inde0
Cost ∈ 2013= cost ∈ 1998  (  )
1998 inde0

6nde* in 1>>( [ #>0

6nde* in 201# [ 3(#.3

&ost of $00m2 [ ;1.(4 million


0.6
2 588.7
Cost of + " = N 1.84 "illion (   ) = N  2.1 "illion
500

 683.6
cost of   2013= N  2.1 "illion   = N   3.68 "illion
390

STACK GAS HEATER

1>>(
0.6
2 2.03
Cost ∈ + " = N 1.84 "illion (  ) =0.068 "illion
500

683.6
cost of   2013= N  0.068 "illion   = N   0.119 "illion
390

CONVERTER

&ost inde* 201# [ 3(0.1

&ost inde* 1>>0 [ #>0


 

13(

Uolume [ 300 gallon

&ost for 300 gallon in 1>>0 [ 1+000


0.6
1000000
Cost of   1 "illiongallon ∈ 1990=17000  (   ) = ! 1.4$+ million
600

680
Cost ∈ 2013= ! 1.457 ( )=! 2.541 "illion
390

COMPRESSOR

6n 1>>0
cap 1
&ost of e@1 [ cost of e@2 ( cap 2 ) 0.3

 7294
&ost of e@1 [ 2100  ( 447.8 ) 0.3

&ost of e@1 [  1120#.4


costinde0 2013
( )
&ost in 201# [ cost in 1>>0 costinde0 1990

928.1
cost in 201# [ 1120#.4 ( )
756.3

[ 1#+4(.4

[  2.2 million

&ost for nitric acid storage tan"



Hiven volume of the tan" at 1>>0 [ 12  1303 gallons

&ost at 1>>0 [ 1+0000

&ost inde* at 201# [ 3(#.3

&ost inde* at 1>>0 [#>$


 

13>

Uolume of storage tan" [2(.#m# to liters [2#(00l

)or $000 gallons


  5000
 ( ) 0.3
&ost at 1>>0 [ 1+0000 12  10
6

13#+.>3 [ 2(#0.$3

[ 44+22(
683.6
 ¿
&ost in 201# [ 1$>#.#>A 395

[ 2(#0.$3

[ ;44+22(.00

)or year 2003


capacity of equip"ent 1
&ost of e@uipment 1 [ cost of e@uipment 2   ( capacity of equip"ent  2 )

)or year 2003


cost ∈ 2006 CP& ∈ 2006
cost ∈ 2013  [ CP& ∈ 2013

RATIO METHOD

&ost of designed plant [ cost of previous plant


capacity of designed plant 
(  ) n
capacity of previous plant 

1200
&ost of 1200tons per day [cost of 2(0 per day   ( 280
 ) 0.3

[ 30 million  (  )
1200
280
0.3
[ 144 million
 

1+0

[2# billion

STEP COUNTING METHOD

& [ 14000 ; \ 0.31$

; [ 1#Anumber of functional unitsC

\ [ 400000 tonsyr Acapacity of plantC

& [ 14000  13  ( 400000 ) 0.31$


[ $0+ million

[  +>.( billion

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