I.

Introduction

For several years, process flow diagrams are commonly used in many chemical

engineering plant designs in order to show the sequence of equipment and unit operations

involved in the overall process, principally to simplify visualization of the manufacturing

procedures and indicate the quantities of materials and energy that were transferred.

In this chapter, the combined detail type of process diagram for the production of nitric

acid from air is presented based on the various data collected from the previous chapter. This

diagram indicates the flow of material (from feed to product), the necessary equipments (major

and minor), the operating parameters (temperature, pressure, etc.), and the quantities of materials

required for the entire process. Furthermore, the subsequent parts of this chapter provide

equipment specifications and available detailed information on flow composition.

Air is obtained in large amounts freely, and it will be used as the major raw material in

the production of nitric acid. The spent coffee grounds will be prepared as a combustion fuel in

the process. On this design paper, the spent coffee grounds having a composition of 53.6

55.43% carbon, 7.77 8.87% hydrogen, 2.17 3.14% nitrogen, and 32.53 36.46 % oxygen;

would enter the furnace to undergo combustion and be used as a fuel.

Spent coffee grounds will be combusted in a vacuum furnace with compressed air. As

the combustion process takes place, exhaust gases are formed such as COx and NOx in which

the latter is needed in the production of nitric acid. During combustion, the fuel undergoes

devolatilization forming carbon particles (containing ash), then these carbon particles react with

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CO2 from the layer below producing CO, then the carbon particles falls to the oxidation zone

forming CO2 leaving ash. As such, particles that are reduced to a wide range of 101,000 m or

more in order to accomplish complete burnout in typically a furnace with 315- 371 oC range of

temperature.

The COx and NOx produce in the combustion will now undergo an absorption process

where it is separated from the flue gas by passing the flue gas through a continuous scrubbing

system. Scrubber will be used for this process. Furthermore, 90.19 92.73% of the COx feed

will be absorbed and all the NOx feed will be present in the exit stream for further reaction in the

oxidizer reactor.

The NOx will react with oxygen to convert all NO to NO2. The NO2 will be converted

to N2O4, and it will proceed to the condenser. The temperature and pressure will determine the

distribution of NO2/N2O4 and the residual amounts of NO and N2O. The rate of oxidation of

nitrogen monoxide is dependent to the temperature, the relationship between the two, is as the

temperature increases the rate of oxidation decreases. In the condenser, the decarbonized gas will

be cooled for the equilibrium reaction to shift towards the formation of dinitrogen tetroxide.

Then, it will proceed to hydrolyzer where NO2 and N2O4 absorbs water to form red nitric acid.

Absorber constraints limit the amount of HNO3 that can be absorbed. In addition, some NO will

form as a by-product of the HNO3 formation reaction. The pressure of absorption is same to the

operating pressure of the combustion and oxidation. Then, to remove the dissolved gases in the

red nitric acid, bleaching with secondary air will be done. After the said process, 55-65% of

113
nitric acid will be produced. The storage temperature will be kept at less than 30 oC to avoid the

vaporization of the product.

The necessary information from the prior chapters related to the major and minor

processes involved and unit operations are presented in this section. In addition, the overall view

of the manufacturing process of Nitric acid from air using spent coffee grounds as oxygen

remover further discussed and shown together with the process flow diagram.

114
115
 III. Detailed Process Description

Equipment Code: D-1

Equipment Name: Storage Tank

Spent coffee grounds (SCG) collected from the manufacturers of instant coffee is stored

at 25C. The spent coffee grounds that will be used in production of nitric acid is fairly

homogenous substrate and relatively free from extraneous materials. The spent coffee grounds is

stored in a clean container and placed in a cool and dry room. Moisture absorption may lead to

physical changes producing wet spent coffee grounds.

In Fischers et.al (2015) work, spent coffee grounds were explored as a feedstock to

engineering alternative processes for the production of valuable chemicals, commodities, or

fuels. SCG was subjected to pyrolysis at slow heating rates. Elemental analysis of SCG shows a

116
composition of carbon, hydrogen, nitrogen and oxygen at 53.6, 7.77, 2.17 and 36.46 percent,

respectively.

From the journal entitled Valorization of Coffee Grounds for Biodiesel Production by

Ndia S. Caetano (2015), the spent coffee grounds were characterized for their moisture content

(12.1 wt. %), total carbon (TC) and total nitrogen (TN) (55.43 and 3.14 wt. % respectively),

cellulose and total lignin contents (33.63 wt. % and 13.81 wt. % respectively), carbon/nitrogen

mass ratio (C/N = 24.8) and higher heating value (HHV, of 19.3 MJ/kg).

According to Perrys ChE handbook 7th edition (2007), Atmospheric tank applies to any

tank that is designed to be used within plus or minus several hundred Pascal (a few pounds per

square foot) of atmospheric pressure. It may be either open to the atmospheric or enclosed.

Minimum cost is usually obtained with a vertical cylindrical shape and a relatively flat bottom at

ground level.

API Standard 2000, Venting Atmospheric and Low Pressure Storage Tanks, gives practical

rules for vent design. The principles of this standard can be applied to fluids and other petroleum

products. Sometimes vents are manifold and led to a vent tank. (Perry and Green, 1997)

117
Equipment Code: C 1

Equipment Name: Air Compressor

To F-1

Air enters the compressor at ambient condition (25C, 1 atm). The air will be compressed

up to 7 - 9 atm. This pressure range is based on the operating pressure of the next equipment

where the compressed air will be used for combustion. Compressed air has the same composition

of the entering stream: nitrogen (78.08-79%), oxygen (20.95 - 21%). Compression must be done

to reduce the volume of feed air.

According to Prof. Shakhashiri (2007) in his article entitled, Gases of the Air,

published in Chemical of the Week, accessed through www.scifun.org, air is composed of

78.08% nitrogen, 20.95% oxygen, and the remaining 0.97% is for the traces of argon, carbon

dioxide, neon, helium, methane, krypton, nitrogen oxide, hydrogen, xenon, and ozone.

118
 Also, in the website of Department of Energy, an article published stating that air is made

up of 21% oxygen, almost 79% nitrogen, and less than 1% other gases. During airfuel

combustion, the chemically inert nitrogen in the air dilutes the reactive oxygen and carries away

some of the energy in the hot combustion exhaust gas. (Retrieved

www.oit.doe.gov/bestpractices/library.shtml, 2015) The operating pressure of the compressors

ranges from 2 bars (2.0265 atm) up to 13 bars (13.17225 atm). (Perry, 2007) The compressor

outlet temperature ranges from 80 to 176.6C. (http://www.ecompressedair.com/library-

pages/aftercoolers.aspx, 2015) There are two process used according to modern nitric acid

plants, the mono-pressure and the dual pressure process. Mono-pressure can be medium- or high-

pressure. In the medium-pressure process, compressors operate at 6 - 10 bar abs (6.08-10.13 atm

abs). With this plant type, it is possible to produce one type of nitric acid with a maximum

concentration of 65%. For high-pressure process, a radial multi-stage compressor can compress

the process air to a final pressure of 8-12 bar abs. Another process is the dual-pressure, which

can compress the process air to a final pressure of 4-6 bar abs. Acid concentrations of more than

68% can be achieved.(http://www.thyssenkruppindustrialsolutions.com/fileadmin/documents

/brochures/uhde_brochures_pdf_en_4.pdf, 2015)

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Equipment Code: F-1

Equipment Name: Furnace

From C-1

To T-1

From D-1

To Waste

Compressed air composed of nitrogen, oxygen, argon carbon dioxide, neon, and helium is

charged into the furnace at a pressure of 7 9atm. Spent coffee grounds will act as a fuel. It will

be burn with a temperature range of 315 371 degrees Celsius.

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 Charging the air to the furnace, the combustion of elemental species proceeds as follows:

C + O2 CO2

C + O CO

N2 + Ox NOx

Flue gas composition results to 69.72 72.62% nitrogen, 13.36- 16.23% carbon dioxide,

10.91-11.15% oxygen, <0.20% carbon monoxide, < 0.30% nitrogen oxide, <0.27% nitrogen

dioxide, and <0.029% flying ash. Combustion of SCG resulted an ultimate analysis of the refuse

of 23.22 40.98% carbon, 33.02-59.02% hydrogen, <5% nitrogen, and <30% oxygen.

The air to fuel ratio of 1.5:1 was obtained which shows that 60% of air was consumed for

every 40% of fuel combusted. (Cholakov, et. al, 2013)

In the combustion of spent coffee grounds, it was found out that there's a high amount of

COx present during the combustion, with compositions as stated, CO 19.9-21.3%,CO <

0.0074 %,O 10.45 - 12.8%,N 62.4 -66.09%,NO < 0.0013%,NO - < 0. 0027%, the rest is

ash. The solids recovered on the combustion has the following composition: C 73.81 81.11%,

H 5.44 2.85%, N 2.16 4.17%, Ash 2.35 -5.23 %. (Pilusa, Herbet, & Muzenda, 2013).

Also, burning the spent coffee grounds typically yields only 93% combustion, that is 7 g

of 100g spent coffee grounds combusted is in ash. This ash formed usually contains free

hydrogen, around 60% of the hydrogen from the spent coffee grounds (Silva et. al, 1998).

According to the website http://www.alentecinc.com/papers/NOx/The%20formation

%20of%20NOx_files/The%20formation%20of%20NOx.htm(2015), Nitrogen oxide production

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is highest at fuel-to-air combustion ratios of 57% O2 at 2545% excess air. Lower excess air

levels starve the reaction for oxygen, and higher excess air levels drive down the flame

temperature, slowing the rate of reaction. A further rise in temperature causes a rapid increase in

the rate of NOx formation.

In the patent entitled Coffee grounds-based fuel and method of manufacture publication

number US 8439988 B2 invented by White and Burns (2015), states that, the grounds are

burned in a pile which is blasted with high temperature of about 600 to 700F (315 - 371C)

combustion air. The quantity of combustion air required to complete combustion in this manner

is about 150% of the stoichiometric air requirement.

In a study, it was found out that using also 7-9 atm for combustion, oxidation and

absorption processes would give 57 60% nitric acid. (Connor, 1987) Spent coffee grounds were

combusted in a 25 kW industrial furnace type hot bag which is a fully automatic heating system

with carbon monoxide, nitrogen dioxide and particle emissions from the combustion (Waelti &

Keller 2009). Furthermore, the efficiency factor of the furnace used for the combustion coffee

ground pellets is estimated to be equal to 0.85 (Salerno et. al. 2001).

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Equipment Code: T-1

Equipment Name: Decarbonizer

From G-1

From F-1

To Waste

From the furnace, COx and NOx produced will then be scrubbed in an adsorption bed.

An adsorption tower will be used for this process with a working condition of 7 9 atm and a

temperature range of 315 371C and a fan will be used to drive the combustion gases into the

decarbonizer. The adsorption of COx in the wet scrubber is 99.70-99.91% of the feed from the

combustion furnace. The exit stream consists of 0.049% CO & CO2, 12.94-13.03% O2, 80.45-

86.97% N2, <0.36% NO, and <0.38% NO2.

The capture of carbon dioxide by adsorptive processes is mainly based on preferential

adsorption of this gas on a porous adsorbent. Thus, the first and most important step is to find a

suitable adsorbent. In industrial processes, zeolite is frequently used as an adsorbent due to its

123
high adsorption capacity. For any such case, the basic information required is the adsorption

equilibrium behavior of the pure components, in this case carbon dioxide. The design of a PSA

system also requires the development of a model that can describe the dynamics of the

adsorption on a fixed-bed with the selected adsorbent. (Dantas, 2011)

Because aqueous amine adsorption processes exhibit some disadvantages such as

low contact area between gas and liquid, low CO2 loading, and severe absorbent corrosion, solid

adsorption process may be an alternative to achieve the CO2 capture purpose. Though the rate-

limiting step for adsorption as the diffusion of CO2 from flue gas to the inside pore of a

mesoporous adsorbent is about 3 orders of magnitude higher than that for aqueous amine

absorption as the CO2 mass transfer across the gas-liquid interface, some existing problems

including low CO2 adsorption capacities at low pressures and influenced by water vapor and

gases other than CO2 still hinder the practical application of adsorption to capture CO2. (Khatri et

al., 2005),

Zeolites as the physical adsorbents for CO2 capture have also been reported. The

adsorption efficiencies of zeolites are largely affected by their size, charge density, and chemical

composition of cations in their porous structures. Accordingly, a number of reports focus on

zeolites with highly crystalline structure, high surface area, and 3-dimensional pore structures by

altering their composition as Si/Al ratio. Another research field focuses on the exchange with

alkali and alkaline-earth cations in the structure of zeolites to enhance the CO2 adsorption.

(Wang et al., 2011)

Zeolite A: 5A (0.80 CaO: 0.20 Na2O: 1 Al2O3: 2.0 0.1 SiO2: x H2O) is used for

separation of normal paraffins from branched-chain and cyclic hydrocarbons; removal of H2S,

CO2 and mercaptans from natural gas.(http://www.sigmaaldrich.com/chemistry/chemical-

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synthesis/learning-center/technical-bulletins/al-1430/molecular-sieves.html#sthash.

pszcAW7g.dpuf)

In reference to Engineering and Design Adsorption Design Guide (March 2001). The

equipment and units needed in the adsorption process depend on the application. A typical

process train consists of piping from the source of the volatile emission stream, such as vapor

emissions from a soil vapor extraction unit, an induced draft blower to control the flow rate, a

heat exchanger, to raise or lower the temperature of the vapor stream (to adjust relative

humidity), and carbon adsorption vessel or vessels.

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Equipment Code: G1

Equipment Name: Pre-Heater

From T-1 To R-1

Decarbonized flue gas from equipment T-1 (decarbonizer) with the temperature range of

315C 371C, is then fed to a heater to elevate the temperature to <700C, near the temperature

requirement of the succeeding process, which is the oxidizer. The entering and exit streams have

the same concentration.

An electric heater is an electrical device that converts electric current to heat. Electric

process heaters are designed for heating flowing liquids and gases, such as: air, nitrogen, steam,

water, oil, flue gas and chemicals. Each circulation heater unit consists of a flanged immersion

heater mounted in an ASME code-designed heating chamber. The chamber is equipped with

flanged inlet and outlet connections, mounting studs, high temperature insulation and an

aluminum jacket (http://www.heat-inc.com/electric.html). Multi-stage design can reach up to

700C operating temperature

126
(http://www.axflow.com/local/norge/produkt%20datablader/instrument/elmess/elmess%20electri

cal%20flow%20heaters.pdf)

The heating element inside every electric heater is an electrical resistor, and works on the

principle of Joule heating: an electric current passing through a resistor will convert that

electrical energy into heat energy. Furthermore, in radiant electrical heaters, the heating elements

are arranged in a reflector. This allows the radiation to be more accurately directed towards the

target area pre-heating up to ladle temperatures of 1500C.

(http://www.kanthal.com/PageFiles/14540/Kanthal_electrical_ladle_heaters_S-KA074-PS-

ENG_LR.pdf)

127
Equipment Code: R1

Equipment Name: Oxidizer

From G-1 To G-2

Pure Oxygen

From D-2

The stream from G-1 (pre-heater) which is the pre-heated de-carbonized flue gas

containing NO and NO2, nitrogen (N2), oxygen (O2), and CO and CO2, will be fed to the oxidizer

together with the compressed oxygen. The NO and NO2 and nitrogen gas will then react with

oxygen.

N + O 2NO

2NO + O2 2NO2

2NO2 N2O4

The exiting stream which is the decarbonized flue gas consists of 55.98-58.04% NO,

27.95-29.05% NO, <2.92% NO and 9.68-12.91% free O2. The operating temperature for this

equipment will range from 700 C to 900 C, and the operating pressure will range from 7-9 atm.

128
 According to Matasa and Tonca (1979), the value of carbon dioxide is very low therefore

it is considered as negligible, therefore the exiting stream which is the decarbonized flue gas

consists of 54.89 - 68.55 % NO, 14.32 - 16.56 % NO, and 1.21 4.47 % NO and 13.68

26.32% free O2.

The operating temperature for this equipment will range from 700 C to 900 C, and the

operating pressure will range from 7-9 atm. (Johnston, 1964).

From S.Suresh and S. Sundaramoorthy, At times, for certain reactions, the activation

energy is so high and the rate so low, that the reaction may be considered as infeasible for all

practical purposes. For example, the activation energy involving reaction between N2 and O2 in

the atmospheric air is so high that the reaction is infeasible at ambient temperature. However, if

the atmospheric air gets exposed to a very high temperature of around 800-1,000C, N2 will react

with O2 to produce oxides of N2 (NO/NO2/N2O), as the rise in the temperature would

substantially increase the rate of reaction.

Le Chateliers principle predicts that the equilibrium will move towards NO2 at high

temperatures and to N2O4 at high pressure specifically the equilibrium is complete towards NO2

at 137C (http://media.rsc.org, retrieved on December 2015).

129
 In addition, Pastil and Wang (2015) said the Gibbs free energy for producing nitric oxide

from direct reaction of nitrogen and oxygen is 86.55 kJ/mole, which is >>0, indicating that it is

very difficult for the reaction to proceed. Therefore, operating the tubular reactor in non-

equilibrium conditions could be one of the possible solutions. The N2 in entering flue gas is

passed through an electrode to excite the molecules, before passing through the catalyst bed. The

catalytic materials reported are tungsten oxide, molybdenum oxide, etc., with tungsten oxide

being the most convenient catalyst. In another patent, OHare claims a process which uses low

frequency high voltage electric arc discharge in combination with catalyst, where the electric arc

was formed entirely within the catalyst bed. OHare claims that these catalysts also act as a

shielding material to avoid dissociation of the product formed, from UV radiation generated by

electric excitation.

Moreover, Conner (1987) said that, using also 7-9 atm for combustion, oxidation and

absorption processes would give 57 60% nitric acid. After the process of the oxidizer, the

temperature of the stream is 700-900C. (Retrieved February 11, 2015

from:http://www.procal.com/images/looptb3/nitric_acid_plants.pdf)

130
Equipment Code: D2

Equipment Name: Oxygen Tank

To R-1

Pure oxygen (>99%) stored in a pressurized cylinder (D-2) is fed to R-1, the oxidizer.

The pressure inside the tank is 7-9 atm.

The oxygen to be used in oxidation is of >99% purity. Gaseous oxygen is colorless,

odorless, tasteless, and nonflammable. It is a strong oxidizer that combines readily with many

materials to form oxides. Oxygen will react with nearly all organic materials and metals. Some

materials react explosively if they come into contact with pure oxygen at high pressure.

(http://www.hse.gov.uk/pubns/hse8.pdf, 2015)

According to the site http://www.esabna.com/euweb/oxy_handbook/589oxy3_18.htm

(2015), the standard oxygen cylinder tank that contains 6.5 m3 at a temperature of 20C will have

131
a pressure of 150 atmospheres. And in the site http://avogadro.chem.iastate.edu (2015), these

cylinders temperatures should not exceed 52 C or 125 F.

Furthermore, according to The Linde Groups product safety assessment data sheet

(2015), the common 2200 psig, 244 ft3 oxygen cylinder weighs about 150 lbs., depending on the

grade of steel used in the cylinder body. Each cylinder has a valve on top and a steel cap that

screws over the valve to protect it from damage. Each valve has a safety device designed to

release pressure if the cylinder pressure becomes too high. If the valve of a high-pressure gas

cylinder is broken off, the contents of the cylinder may jet from a hole about inches in

diameter. The escaping gas could have enough thrust to turn the cylinder into a rocket,

depending on the cylinders size and weight. Also, oxygen containers are equipped with

pressure-relief devices to protect from over pressurization and possible rupture.

Oxygen must be stored in the pure state as a gas and in seamless containers of drawn

steel plates. Storage must be equipped with a high pressure valve made of bronze. Valve should

be completely open, if not, high pressure could cause the valve to leak. Valve has a safety device

to drain oxygen slowly in the event of high temperatures.

(https://www.dmme.virginia.gov/dmm/PDF/TRAINING/REFRESHER/MaintenanceRepairTopi

cs/AR-oxygen-acetyleneuseandsafety.pdf, 2015)

132
Equipment Code: G-2

Equipment Name: Cooler-Condenser

To R-2
From R-1

To R-2

The dinitrogen tetroxide gas from R-1, which is the oxidizer, with a temperature of 700 -

900C, enters the cooler-condenser to be cooled down to 25 to 40C. The exit stream which is a

nitrogen dioxide-rich gas comprises of 62.58-62.63% NO2, 6.36-6.38% NO, 30.94-31.031% O2,

<0.043% CO2 and CO. The condensate is composed of 98.62-98.67% N2O4, and 1.34-1.36%

water. The condenser operates at a pressure range of 7 to 9 atm.

From the oxidizer, which at this point has a temperature of 700-900C, the product is

passed through a cooler-condenser where it is further cooled to 38C at pressures up to 7.79 atm

abs. (http://www.procal.com/images/looptb3/nitric_acid_plants.pdf, 2015)

133
 Operating temperature of the cooler condenser ranges from 20 40 degrees Celsius.

(Johnston, 1989).The gas is then cooled down to 37.7 degrees Celsius or 100 degrees Fahrenheit

to achieve a 60 % maximum conversion of N2O4. The operating pressure is 116 psia or 7.89 atm.

(www.epa.gov, 2015). The effect of cooling on the equilibrium system N2O4 - NO2 at <100C

liquefies the dinitrogen tetroxide (Masterson and Hurley, 2000).

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Equipment Code: R - 2

Equipment Name: Hydrolyzer

From G-2

To T-2

R-2

From G-2

From the cooler condenser, the cooled NO2 rich gas enters the bottom section of the

tower while the dinitrogen tetroxide rich condensate enters the column at a higher point. The

entering streams will be absorbed and reacted in the hydrolyzer, R-2. The column operates at a

pressure range of 7atm to 9 atm and a temperature range of 25C to 35 C. The exiting stream

from the column consists of HNO ranging from 55.69 60.01%, 33.98 39.99% water, and

less than 7.33% impurities. The reaction gives off a tail gas composition of 12.85 73.47%

135
dinitrogen tetroxide, < 8.0% nitrogen dioxide, < 15.97% nitric oxide and <0.114% carbon

oxides. This product is reddish to brownish in color due to the presence of dissolved NOx.

In a discussion of Miller (1987), it is stated that reaction of water to di-nitrogen tetroxide

can produce nitric acid as main product nitric oxide as by-product. The gas mixture obtained by

oxidation of nitrogen dioxide, containing nitrogen oxide and dinitrogen tetroxide, is reacted with

water as follows:

3NO2 + H2O 2HNO3 + NO H=-73 KJ/mol

N2O4 + H2O HNO3 + HNO2 H=-65 KJ/mol

71.1% of the dinitrogen tetroxide is converted to nitric acid while 98.52% of nitrogen

dioxide in the reaction gas is converted to nitric acid. (Gais, 2013)

The temperatures at exit streams of the absorption reactor is about 20-40 C.

(Wiesenberger, 2001). The operating pressure range of 7-9 atm for combustion, oxidation and

absorption of water would yield 57 60% nitric acid. (Conner, 1987)

In the book entitled, Chemical Engineering Design Project: A Case Study Approach,

Topics in Chemical Engineering, Volume 6 by Martin S. Ray and David W. Johnston, (1989),

the absorption reactor is designed to achieve a range of 55.69 60.01% nitric acid, with 33.98

39.99% water, and the remaining is for the dissolved gases. This product is reddish in color due

136
to the presence of the dissolved gases. The operating pressure and temperature of this process are

9 atm and 20-40 degrees Celsius.

Absorber performance is controlled by temperature and pressure. Lower temperatures

improve the absorption rate and increase the acid concentration. (UN Industrial Development

Organization, International Fertilizer Development Center, 1998)

137
Equipment Code: T 2

Equipment Name: Bleaching Tower

From R-2

To D-4

T-2

From C-2

Red nitric acid enters the bleaching column at a temperature of 30 degrees Celsius and at

a pressure range of 7-9 atm. The bleaching towers main function is to remove dissolve NOx in

the red nitric acid. The red nitric acid will be pumped to the tower and the dissolved oxides are

then stripped from the red nitric acid using air in a bleaching column while the O2, N2 and N2O4

will be subjected to treatment. The compressed bleach air stream enters the column at pressure

limits of 7-9atm and at a temperature of approximately 80C. Tail gases leave the bleaching

column with a composition of 9.89% dissolved N2O4, and the nitric acid product at 55 - 65%

concentration leaves at a temperature range of 45- 55 degrees Celsius. The resulting nitric acid

product is then transported to the nitric acid product storage tank.

138
 Nitric acid formed in the absorber is usually routed through an external bleacher where

air is used to remove (bleach) dissolved oxides of nitrogen (US EPA, 1991). The remaining

unabsorbed NOx is vented from the top while bleached nitric acid is withdrawn from the bottom

of the tower.

In the book entitled, Chemical Engineering Design Project: A Case Study Approach,

Topics in Chemical Engineering, Volume 6 by Martin S. Ray and David W. Johnston,

published in year 1989, the bleaching tower is described to remove the dissolved gases in the

nitric acid using air. This dissolved gases is responsible for the red color of the product. The

operating temperature ranges from 45 55 degrees Celsius. Pressure of the operation is 9 atm

maximum. The exit product is expected to be 55-65% HNO3, and the tail gas is composed of air

and dissolved gases (9.89% concentration) from the red nitric acid.

The bleaching column is a smaller sieve tray-type column. Impure acid runs down the

column from the top tray and air is bubbled up through the liquor to remove dissolved nitrogen

oxides. The acid from the base of the column is the final desired 60%(wt.) product. The air-feed

ratio in the bleaching column is 1:2. (Johnston, 1989)

Same idea was discussed by Hocking, published 1998. He pointed out that nitrogen

dioxide gas may also be present to the product nitric acid, which gives the acid a brown/red

color. This nitrogen dioxide is stripped from the product acid by purging the last few plates of

the absorber with bleach air, to give a colorless pale yellow product acid containing 60-62% by

weight HNO3 as the bottom product of the absorber. The bleach air, at the same time as striping

excess dissolved nitrogen dioxide from the product.

139
Equipment Code: C 2

Equipment Name: Air Compressor

To T-2

Air, composed of nitrogen (78.08-79%) and oxygen (20.95-21%); enters the compressor

at ambient condition (25C, 1 atm). The air will be compressed up to 7 to 9 atm. This pressure

range is based on the operating pressure of the next equipment where the compressed air will be

used for bleaching. Compressed air have the same composition of the entering stream. The

compressed air will be fed to bleaching tower to strip the dissolved nitrogen oxides from the acid

solution

According to Prof. Shakhashiri in his article entitled, Gases of the Air, published in

Chemical of the Week (www.scifun.org), Air is composed of 78.08% Nitrogen, 20.95% Oxygen,

and the remaining 0.97% is for the traces of Argon, Carbon dioxide, Neon, Helium, Methane,

Krypton, Nitrogen oxide, Hydrogen, Xenon, and Ozone. (2007) Also, in the website of

Department of Energy, an article published stating that air is made up of 21% oxygen, almost

140
79% nitrogen, and less than 1% other gases. During airfuel combustion, the chemically inert

nitrogen in the air dilutes the reactive oxygen and carries away some of the energy in the hot

combustion exhaust gas. (Retrieved www.oit.doe.gov/bestpractices/library.shtml, 2015)

The operating pressure ranges from 2 bars or 2.0265 atm up to 13 bars or 13.17225 atm.

(Perry, 2007) the compressor outlet temperature ranges from 80 to 176.6C.

(http://www.ecompressedair.com/library-pages/aftercoolers.aspx)

There are two process used according to modern nitric acid plants, the mono-pressure and

the dual pressure process. Mono-pressure can be medium- or high-pressure. In the medium-

pressure process, compressors operate at 6 - 10 bar abs (6.08-10.13 atm abs). With this plant

type, it is possible to produce one type of nitric acid with a maximum concentration of 65%. For

high-pressure process, a radial multi-stage compressor can compress the process air to a final

pressure of 8-12 bar abs. Another process is the dual-pressure, which can compress the process

air to a final pressure of 4-6 bar abs. Acid concentrations of more than 68% can be achieved.

(http://www.thyssenkruppindustrialsolutions.com/fileadmin/documents

/brochures/uhde_brochures_pdf_en_4.pdf, 2015).

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Equipment Code: D-3

Equipment Name: Product Storage Tank

From T-2

After bleaching, the 60% nitric acid produced is stored in a storage tank. The product

storage temperature must be kept below 30C to avoid vaporization. Storage pressure is at

atmospheric pressure up to 1.36 atm. (http://zchpolice.grupaazoty.com/en/oferta/

chemikalia/27/34, retrieved on March 2015)

A pressure relief valve is attached to the roof. This valve is opened automatically when

pumping product to, or withdrawing product from, the tank. The valve is shut when pumping

stops so that vapor losses from the tank are contained. (Ray and Johnston, 1989)

Stainless steel type 304 is usually used for concentrations up to 95%. Nitric acid up to

and including 99 percent strength is stored in stainless steel equipment. Each storage tank should

be provided with a vent of sufficient size and discharging at a safe location.

(https://law.resource.org/pub/in/bis/S02/is.4560.1968.html)

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