Assignments

1. Explain shrinking and swelling effect in boilers.

2. Discuss safety system used for CO2 Compressor, major engineering
problems in urea plants. Discuss Process variables affecting
conversion of urea in reactor.
3. Different CO2 absorption processes.
4. Explain Reduction techniques of green house gases in industries.

Q1. Explain shrinking and swelling effect in boilers.

Dynamic shrink/swell is a phenomenon that produces variations in the level of the liquid
surface in the steam drum whenever boiler load (changes in steam demand) occur. This
behaviour is strongly influenced by the actual arrangement of steam generating tubes in the
boiler.

Water wall boilers with radiant tubes on three sides of the firebox, There is a steam drum
located above the combustion chamber and a mud drum located below the combustion
chamber. During operation, the tubes exposed to the radiant heat from the flame are
always producing steam. As the steam rises in the tubes, boiler water is also carried upward
and discharged into the steam drum. Tubes that are not producing significant steam flow
have a net downward flow of boiler water from the steam drum to the mud drum.

The tubes producing large quantities of steam are termed risers and those principally
carrying water down to the mud drum from the steam drum are termed down-comers.
Excluding the tubes subject to radiant heat input from the firebox flame, a given tube will
serve as a riser at some firing rates and a down-comer at other firing rates.

The mechanics of the natural convection circulation of boiler water within the steam
generator is the origin of the dynamic shrink/swell phenomenon. Consider what happens to
a boiler operating at steady state at 600 psig when it is subjected to a sudden increase in
load (or steam demand).

A sudden steam load increase will naturally produce a drop in the pressure in the steam
drum, because, initially at least, the firing rate cannot increase fast enough to match the
steam production rate at the new demand level. When the pressure in the drum drops, it
has a dramatic effect on the natural convection within the boiler. The drop in pressure
causes a small fraction of the saturated water in the boiler to immediately vaporize,
producing a large amount of boil-up from most of the tubes in the boiler. During the
transient, most of the tubes temporarily become risers. The result is that the level in the
steam drum above the combustion chamber rises.

However, this rise in level is actually an inverse response to the load change. Since, the net
steam draw rate has gone up; the net flow of water to the boiler needs to increase, because
the total mass of water in the boiler is falling. However, the level controller senses a rise in
the level of the steam drum and calls for a reduction in the flow of feed-water to the boiler.

This inverse response to a sudden load increase is dynamic swell. Dynamic shrink is also

observed when a sudden load decrease occurs. However, the dynamic shrink phenomenon
does not disrupt the natural convection circulation of the boiler as completely as the
dynamic swell effect. Consequently, the reduction in level produced by a sudden decrease in
load is typically much smaller and of shorter duration than the effect produced by dynamic
swell.

Control strategy for shrink and swell:

When a sudden load (steam demand) increase occurs, the feed forward portion of the
strategy will produce an increase in the set point for the feed-water flow controller. This
increase in feed-water flow controller set point will be countered to varying degrees by the
level controller response to the temporary rise in level produced by the dynamic swell.

The standard tool used to minimize the impact of the swell phenomenon on the level in a
three-element level control system is the lead-lag relay in the feed forward signal from the
flow difference relay. This is the traditional means of dealing with mismatched disturbance
and manipulated variable dynamics in feed forward systems, and is certainly applicable in
this control strategy. When used in the three-element level control strategy, the lead-lag
relay is commonly termed the “shrink/swell relay.”

There are two significant limitations to the use of the lead-lag relay for shrink/swell
compensation. To begin with, the response of most boilers to a load increase (swell event) is
much more dramatic than the response to a load decrease (shrink event). In other words,
the system response is very asymmetric. The lead-lag relay is perfectly symmetrical in
responding to load changes in each direction and cannot be well matched to both
directions.

Furthermore, the standard method of establishing the magnitudes of the lead time constant
and lag time constant involves open loop tests of the process response to the disturbance
(steam load) and to the manipulated variable (feed-water flow). A step test of the
manipulated variable is generally not too difficult to conduct. However, changing the firing
rate upward fast enough to actually produce significant swell is difficult without seriously
upsetting the steam system, an event that is to be avoided in most operating plants.
Therefore, the practitioner’s only choice is to gather accurate data continuously and wait for
a disturbance event that will exercise the shrink/swell relay’s function.

When a lead-lag relay is to be added to an existing three-element boiler control scheme,

operator knowledge of the boiler behaviour in sudden load increase situations can guide the
initial settings. For example, if the operators indicate that they must manually lead the feed-
water valve by opening it faster than the control system will open it automatically, it is clear
that a lead time constant larger than the lag time is required. Similarly, if the operator must
retard the valve response to prevent excessively high level, the lead time constant must be
less than the lag time. The lag time constant will typically fall in the range of one minute to
three minutes. The ratio of the lead time constant to the lag time constant determines the
magnitude of the initial response to the disturbance. If the ratio is one to one, the system
behaves the same as a system with no lead-lag relay.

Ultimately, the system must be adjusted by watching the response to actual steam system
upsets that require sudden firing increases. If the initial observed response of level to an
upset is a rising level, the ratio of lead time to lag time should be decreased. The inverse is
similarly true. If the recovery from an initial rise in level is followed by significant overshoot
below the level target, the lag time should be reduced. If the recovery from an initial level
drop is followed by a large overshoot above the level target, the lag time should be
increased.

Q2. Discuss safety system used for CO2 Compressor, major

engineering problems in urea plants. Discuss Process variables
affecting conversion of urea in reactor.
CO2 Compressor: CA-1
Reciprocating type 3 stages double acting supplied by M/s Worthington of West Germany.
This is designed to compress CO2 gas from 11kg/cm2 to 243kg/cm2. Intercoolers are
provided on 1st and 2nd stages to remove heat of compression, condensate separators are
provided for removing condensate. Max. Capacity is 17510 nm3/hr. It is driven by
synchronous motor of 2250KW and 300rpm. Lubrication of the compressor is done by a gear
type oil pump. A separate oil pump is provided for the lubrication of the crankcase. Oxygen
and nitrogen are added to the desired concentration in the suction of compressor. 1 st stage
consists of 2 no. of cylinder while 2nd & 3rd stage had 1 no. of cylinder each.

Safety devices:

There are pressure relief valves provided at discharge line each stage of compressor.
Following tripping has been provided for the safety of the compressor:

a) 1st stage low suction pressure- 7kg/cm2

b) Cooling water low outlet pressure- 0.5kg/cm2
c) Low lube oil pressure after last bearing-1.5kg/cm2
d) High discharge temp of 1/2/3 stage- 160/140/1450C
e) Low 3rd stage suction temperature- 340C
f) High compressor bearing temp.(4 pts)- 800C

Water cooling system:

The cooling water enters the battery limit at 4.5kg/cm2 and 330C. Cooling water is used in
motor winding coolers, inter-stage coolers. Oil coolers for cylinders jacket cooling.

Lubrication system:

a) The compressor is provided with one auxiliary rotary pump ( driven by electric
motor) with strainer for feeding oil into lubrication circuit. The oil taken from oil
sump is discharged into the oil cooler from where it enters into the header of the
frame through filter.
 b) The compressor cylinders are lubricated by an injection pump driven by electric
motor. The lubrication system consists of various feed lines which supply oil to the
cylinder and packing’s. Each pumping unit in the lubricator is adjustable to permit
regulation of the feed oil.

Protection devices:

a) Oil pump relief valve: The lubricating oil system is protected from excessive pressure
by a relief value located at discharge side of the oil pump which releases excessive
pressure to the oil pump’s suction line.
b) Oil pressure failure: The lubrication system is protected against oil pressure failure
by pressure switch. An alarm is given first at a pressure of 2kg/cm2 and on further
drop to 1.5l g/cm2, the pressure switch will stop the main motor.

No. of Stages Inlet pressure Inlet temp Outlet pressure Outlet temp
With inter- (Kg-f/cm2) (0C) (Kg-f/cm2) (0C)
cooling
1 11 37 32 121
2 31 42 85 126
3 84 48 220 133

MAJOR ENGINEERING PROBLEMS:

1) Carbamate decomposition and recycle:

There are many processes that can be used for the manufacture of urea. Main difference in
competing processes is in the recycle design. Since, conversion is only 40-50 % per pass, the
unreacted off gases must be recirculated or used economically elsewhere. Recompression
of off gases is virtually impossible because of corrosion and formation of solid carbamate in
compressors.

2) Production of granular urea:

Biuret formation is another problem. Vacuum evaporation of urea from 80% to about 99%,
spraying to air cool and solidification must be done just above the melting point of urea and
with a minimum residence time in the range of several seconds.

3) Heat dissipation in the autoclave:

The exothermic heat of reaction can be removed by coils or wall cooling.

4) Corrosion:
This has been the major reason why the NH3-CO2 process was slow to develop. High cost
silver or tantalum liners are used in the autoclaves with hastealloy C, titanium, stainless
steel (321 SS), and aluminum alloys used in other parts of the plant. Minimum pressure and
temperature conditions with excess NH3 are desirable to reduce the severe corrosion rates.
Under these conditions, stainless steel can be used in the autoclave.

Urea reactor (new)

Volume-33m3, No. of trays-9, Type of trays- High eff. Casale trays, weepholes- 14

Temp. Bott/Top- 193/1980C, Pressure-220kg/cm2, Liner- 2RE69, Thickness- 6mm,

Mole ratio (NH3/CO2) =3.1, Mole ratio (H2O/CO2) =0, Urea conversion w.r.t. CO2 =72

Urea reactor (old)

Volume-50m3, No. of trays-14, Type of trays- High eff. Casale trays, weepholes- 28

Temp. Bott/Top-188 /1980C, Pressure-220kg/cm2, Liner- SS316L, Thickness- 12mm

Mole ratio (NH3/CO2) =2.9, Mole ratio (H2O/CO2) =0.7, Urea conversion w.r.t. CO2=53%.

THE VARIABLES THAT AFFECT THE AUTOCLAVE REACTIONS ARE:

1) Temperature:
Process temperature (185°C) favours equilibrium yield at a given pressure (180 ata). The
conversion of ammonium carbamate to urea gradually increases as the temperature
increases. However, after a particular temperature, depending upon the pressure, the
conversion suddenly drops with further increase in temperature. The pressure
corresponding to this temperature which is usually in the range of 175-185°C, is known as
the decomposition pressure which is about 180 atm.

2) Pressure:
The main reaction is sufficiently slow at atmospheric pressure. However, it starts almost
instantaneously at pressure of the order of 100 atm and temperature of 150ºC. There is
reduction in volume in the overall reaction and so high pressure favors the forward reaction.
This pressure is selected according to the temperature to be maintained & NH3:CO2 ratio.
3) Concentration:
Higher the concentration of the reactants, higher will be the forward reaction according to
the law of mass action. CO2 being the limiting reagent higher NH3:CO2 ratio favours
conversion. Since, dehydration of carbamate results in urea production, lesser H2O:CO2
ratio favours conversion. Water intake to the reactor should therefore minimum.

4) Residence time:
Since, urea reaction is slow and takes about 20 min to attain equilibrium, sufficient time is
to be provided to get higher conversion. Reactor is designed to accommodate this with
respect to the other parameters of temperature, pressure and concentration.

5) H20/C02 Ratio:
Excess water disturbs the urea formation. Excess water recycle reduces the reactor volume
w.r.t to reactants. Too low causes clogging in the system, optimum ratio is 0.4-1.0.

6) Biuret formation:
A problem faced during manufacture of urea is the formation of biuret during the
production of urea. It is not a desirable substance because it adversely affects the growth of
some plants. Its content in urea should not be more than 1.5 % by weight.
2NH2CONH2 =NH2CONHCONH2 + NH3

Q4. Different CO2 absorption processes.

The CO2 formed in the shift conversion process is generally removed by scrubbing with a
solvent. Conventional CO2 removal applies a chemical absorption method using an
absorbing liquid. The solvents used in chemical absorption processes are mainly aqueous
amine solutions, such as monoethanolamine (MEA), or hot potassium carbonate solutions.
The capture of CO2 with solvents requires mechanical energy to circulate the solvent and
heat to regenerate the solution. The energy consumption of the CO 2 removal system
depends on the solvent used, the way the system is incorporated in the ammonia plant, and
is affected by syngas purity and CO2 recovery.

The solvent monoethanolamine (MEA) has been widely used in the ammonia production
process, but has some significant drawbacks including the considerable amount of energy
required for regeneration. Improved solvents, which require less energy for regeneration of
the solution, include the Benfield process (HiPure and LoHeat) and BASF’s two-stage
activated diethanolamine (aMDEA).

N‐Methyldiethanolamine (MDEA) is a tertiary amine whose amino group is incapable of

reacting with CO2. However, it is alkaline and so is an excellent sink for protons produce by
CO2 hydrolysis. Because it is non‐reactive, aqueous MDEA by itself absorbs CO2 far too
slowly to be an effective solvent for treating ammonia synthesis gas. But when spiked with a
relatively small concentration of piperazine, a diamine that reacts extraordinarily fast with
CO2, the resulting blend is an excellent solvent for treating syngas and removing CO2 in the
production of LNG.

Before looking at specific chemical solvents, it is beneficial to describe the function of an

amine that is completely nonreactive towards CO2, in the CO2 absorption process, and to
give a quantitative picture of how effective piperazine really is, like all amines, tertiary
amines dissociate in water and produce hydroxyl ion:

RN + H2O RNH+ + OH-

The hydroxyl ion is what gives amines their alkalinity. However, CO2 does not react with a
tertiary amino group because this group lacks the mobile hydrogen necessary to exchange
for the CO2 and form carbamate. Instead, the CO2 merely absorbs into water and
hydrolyzes:
CO2 + H2O H+ + HCO3-
The liberated proton is neutralized by the amine’s alkalinity as represented by the hydroxyl
group. Thus, unless one can directly catalyze the hydrolysis reaction itself (as can be done
using carbonic anhydrase, for example), CO2 absorption rates are not enhanced at all by
reaction and will be no faster than they would be into essentially pure water. The function
of the tertiary amine then, is not to enhance absorption rates through chemical reaction but
rather to increase dramatically the capacity of the solvent. The trouble with straight MDEA,
however, is that the CO2 absorption rate is almost always too slow for it to be used alone,
except for bulk CO2 removal at high pressure. It simply cannot be used effectively for the
deep CO2 removal required for syngas and LNG production. The CO2 reaction must be
promoted, and piperazine is an excellent promoter.

Piperazine is a cyclic diamine with the structure. It reacts with CO2 about ten times faster
than MEA. Its second order rate constant at 25°C, for example, is about 59,000 L∙mol‐1∙s‐1
versus MEA at 6,000 L∙mol‐1∙s‐1. This makes piperazine the most reactive promoter of CO2
kinetics available commercially. Over the last 30 years, the aMDEA® process, first patented
by BASF in 1982, has captured the lion’s share of the ammonia syngas purification market,
and it is still used in the majority of the world’s ammonia plants.

In summary then, although MDEA alone can be used for bulk CO2 removal at high pressure,
its reaction rate with CO2 is much too slow for it to be usefully applied to deeper CO2
removal in columns of reasonable height. For that, an activator is required, and piperazine
has evolved as the activator of choice. Today, most solvent vendors offer a form of
piperazine‐promoted MDEA under a variety of brand and code names.

RRʹRʹʹN: + CO2 + H2O RRʹRʹʹ-N-H + HCO3-

MDEA‐Piperazine Composition:

The most commonly used total‐amine strength for generic MDEA and MDEA‐based blends is
50 wt% although, as we shall see, this is sometimes not the best concentration to use.
Figure 4 shows how the relative concentrations of piperazine and MDEA in a 50 wt%
total‐amine blend affect the CO2 left in the treated gas. It is apparent from the figure that
about 4 wt% piperazine is needed to achieve < 1 000 ppmv CO2 and that 5 or 6 wt%
piperazine allows one to achieve in the vicinity of 100 ppmv CO2. The treating performance
is very sensitive to the concentration the piperazine additive and this is why it is so
important to monitor solution strength for piperazine content. Unfortunately, piperazine is
somewhat volatile so its concentration tends to fall with time more rapidly than does MDEA.
Plant performance depends critically on maintaining the right concentrations of the solvent
ingredients.
A potential additional advantage is that the reduction in energy consumption, by using
improved solvents in the CO2 capture process, may allow a reduction in the steam-carbon
ratio in the primary reforming section. Lower reboiler duty also allows for an increase in the
plant capacity without any modification of equipment conventional CO2 removal applies a
chemical absorption method; however CO2 can also be removed using physical absorption.
Physical absorption processes use an organic solvent, which absorbs CO2 as a function of the
partial pressure. The high CO2 loadings result in low circulation rates and less utility costs for
these types of processes. Physical absorption solvents typically used in ammonia production
processes include glycol dimethylethers (Selexol) and propylene carbonate. Regeneration of
the solution is performed by vacuum flashing and air stripping and consumes significantly
less energy than in chemical absorption.

This unit provides process gas free of CO2 (limit 1000 ppm) for the production of ammonia
and necessary CO2 for Urea production. In this unit, CO2 in the process gas is absorbed by
the GV solution in the Absorber, providing process gas with less than 1000 ppm of CO2.
Stripping of the absorbed CO2 is done in the two regenerators and CO2 stripped is supplied
to Urea Plant. CO2 removal section know how is by Giammarco-Vetrocoke of Italy. The
Vetrocoke solution consists of approx. 30 wt. % K2 CO3, Vanadium Pentoxide (V2O5) as
corrosion inhibitor, Glycine and a tertiary amine DEA as activator. The reason for keeping
the solution hot is to increase the rate of absorption and keep the bicarbonate dissolved.

The process gas from the shift reactors is passed to the CO2 absorber. In the absorber the
gas flows upwards against a descending stream of hot potassium carbonate solution.
Approximately 15 percent of the solution is introduced above the top bed at 70 deg. C
whereas the remainder is introduced at about 106 deg C below the two top beds.
The chemistry involved in this unit is chemisorption and is explained as follows:

CO2 + H2O HCO3- + H+ 1

K2CO3 + HCO3- + H+ 2KHCO3 2

K2CO3 + CO2 + H2O 2KHCO3 3

 % 𝑲𝑯𝑪𝑶𝟑
Fractional conversion (Fc) = %𝑲𝟐𝑯𝑪𝑶𝟑+% 𝑲𝑯𝑪𝑶𝟑

The reaction rate of (3) depends on the reaction rates of (1) and (2). Reaction rate of (1) is
slow and the activator activates this reaction by quickly introducing the gaseous CO2 in the
liquid phase. The activator glycine reacts with CO2 and forms glycine carbonate according
to the reaction.

NH2 CH2 COO- + CO2 COO-NH CH2 COO- + H+ 4

COO-NH CH2 COO- + H2O NH2 CH2 COO- + HCO3- 5

In solution regeneration, reaction (3) is reversed by application of heat and pressure

reduction and the lean and semi lean K2 CO3 solution is recirculated for further absorption of
CO2.

Mechanical filtration:
Mechanical filtration is to keep the solution clean and free from solids. These solids
may be impurities of the chemicals used for solution preparation and make-up,
catalyst dust entrained by the process gas, rust from steel equipment particularly after
a long shutdown period or fine dust from poor quality activated carbon. Impurities may
also enter the sump tank accidentally.
Two mechanical filters are provided in the plant. The main filter is placed upstream of the
activated carbon filter in order to protect carbon filter from solid build up. The second filter
(of smaller surface) is placed downstream of the activated carbon filter in order to retain
any fine dust released from poor quality or crashed carbon which can seriously affect the
plant's smooth operation. The filtering medium is polypropylene (alkaline resistant) for
temperature not exceeding 100 ºC. The solution fed to the main filter is about 5% of the
circulating flow while only 50 % of the solution exiting the filter feeds the activated carbon
filter and the downstream mechanical filter.

Activated Carbon Filtration:

This filtration is intended for removing any organic substances (active as well as
degraded organic activators) from the solution. These substances such as grease, lubricating
oil, paints, epoxy resins degraded organic compound etc, are saponifiable by the alkaline
solution. They may cause foaming problems and consequent worsening of the CO2 removal
plant's performance. The carbon filter treats the lean and semi-lean solution streams in
similar way. It is placed downstream of the mechanical filter for extending the carbon life.
Only a fraction (about 50 %) of the solution coming out of the mechanical filter feeds the
activated carbon filter. The most advisable temperature range for the filtration is 70-110 ºC.

Q5. Explain Reduction techniques of green house gases in industries.

NOx gases are potent greenhouse gases. Based on combination of its IR transmission
characteristics and its longevity in the atmosphere it eventually diffuses into the stratosphere,
where it becomes photo chemically active and contribute to ozone depletion. Major sources
of NOx emissions are industrial sources, agricultural soils, manure management.

NOx are the oxides of Nitrogen (N2), which include, NOx especially refers to NO, NO2.

1. Nitrous oxide (NO)

2. Nitrogen dioxide (NO2)
3. Nitrogen oxide (N2O)
4. Di-nitrogen trioxide (N2O3)
5. Di-nitrogen tetraoxide (N2O4)
6. Di-nitrogen pentoxide ( N2O5)

Need for NOx abatement: Due to harmful effect of these gases, environmental regulations
compels to reduce NOx levels in the gases to be vented to atmosphere.

Source of NOx: There are 2 sources of NOx gases in nitric acid plant

 In Burner (combustion section)

4 NH3+5O24NO+6H2O+216.7 kCal ……. (1)
Along with NO, other oxides of nitrogen are produced by side reactions.
 N2O4, N2O5,N2O3 formed are decomposed to NO, N2O,NO2at high
temperature in burner
 NO, NO2are desirable at this stage
 N2O formed is a very stable & undesirable
 At this stage, methods to reduce N2O formation has to be employed without
effecting NO yield

 In absorption towers, NO is produced according to below reaction

3NO2+H2O  2 HNO3+NO+32.5 kCal …… (2)

The concentration of NOx depends on final acid concentration,

i) Absorption tower pressure and design,
ii) Temperatures of the cooling tower water, quantity and quality of process water
iii) Degree of tail-gas treatment, if any.

The following methods may be employed for the existing nitric acid plants.

Increasing absorption tower pressure:

Oxidation reaction is a 3rd order reaction & rate equation is given by
2NO+O2 2NO2+27 kCal …………. (3)
rNO2 = kP*PNO2*PO2
Where PNO, PO2 are the partial pressures of NO, O2 respectively.
 Oxidation reaction is proportional to square of partial pressures of NO& directly
proportional to partial pressure of oxygen .But as absorption proceeds from one
tower to another, concentration of NO decreases which in turn decreases oxidation
reaction.
Hence, if total pressure of tower is increased (say pressure is doubled), then
oxidation also increases (by 8 times) which oxidizes NO formed in reaction of NO2
with water to produce HNO3 & which in turn reduces amount of NOx.
However, it is not needed in high pressure plants, as NOx levels in high pressure
plants are less.

Recycle of NOx from absorption tower to oxidation tower:

We may think of recycling the unconverted NOx to the oxidation tower so that unconverted
NO may be oxidized to NO2& NO2 may be absorbed in absorption tower to produce HNO3.

But, doing so not only increases the operating cost (such as installing pumps, compressors
.etc.& their running costs) but also dilutes the stream which decreases rate as discussed
above in 1 which affects the heat transfer & system pressure. Hence, it is also not an
economical option.

Source Reduction:

Most emissions to the atmosphere can be reduced by plant design and optimal operation.
Makeup and cooling water temperature will affect the absorption stage and hence
emissions of NOx. Process conditions for NH3 oxidation should be high temperature, short
residence time & low pressure to avoid side reactions.

NOx abatement techniques

New high-pressure nitric acid plants can achieve satisfactory emission levels of NOx without
treatment of the gas. Low & medium pressure plants needs treatment. The following
methods or combination of them may be used.

Extended Absorption:

 Installing a single large absorption tower or extending the height of an existing

tower
 Adding a second tower (or more) in series with the existing tower
The increase in volume, no. of trays & residence increases absorption efficiency which
reduces NOx emissions & increases acid yield. N2O is unaffected in this process.
Extended absorption is successfully used in retrofit applications.

Selective Catalytic Reduction (SCR):

  It is one of the most important processes for reduction of NOx. The process is called
‘selective’ because the excess oxygen is not consumed. It can operate at any
pressure. A catalytic bed is installed in between last absorption tower & expander.
Catalyst promotes reaction between NH3& NOx.
In SCR, NOx & N2Oare converted to N2 by reducing it with reagents. These are:

 Hydrocarbons:

NOx reacts with hydrocarbons to form N2 & CO2 as reaction shown below in presence of
Iron-Zeolite catalyst.

2NO+C +H2+0.5O2 N2+CO2+H2O

2NO2+2C+H2+0.5O2 N2+2CO2+H2O

This technology may be applied to all kinds of nitric acid plants but retrofit costs may
behigh. Use of hydrocarbons results in emission of CO, CO2 with excess of heat generated.

 Ammonia:
The reduction reaction is as shown
4NO+4NH3+O24N2+6H2O ΔHr = -408 kJ/mol NO
2NO2+4NH3+O23N2+6H2O ΔHr =-669 kJ/mol NO2

The primary variable affecting NOx reduction is temperature. At too low a temperature, rate
is too low, resulting in ammonia slip(NH3 passing through SCR unreacted). At too high
temperature, NOx exit concentration increases due to oxidation of NH3 to NOx & high
temperature may damage the catalyst. Typically, the operating temperature is in between
420-670 K.

 Urea:
The reactions occurring are nearly equal to those of ammonia. SCR processes in HNO 3 plants
use NH3 whereas SCR units for diesel engines use urea.
4NO+NH2CONH2+O24N2+4H2O+2CO2

Other possible reducing agents include cyanuric acid ((CNOH)3)& ammonium sulphate
((NH4)2SO4). Pure anhydrous NH3 is extremely toxic & difficult to store, but there is no need
to further conversion to operate in SCR. It is favoured by large industrial operators. Aqueous
ammonia is substantially safer to store & transport than anhydrous NH3 but it must be
hydrolysed in order to be used. Urea is safest to store, but requires conversion to NH3
through thermal decomposition in order to be used as effective reducing agent.

The disadvantages of urea are high costs. Cost of catalyst can amount to 40-60% of
operating cost & it is to be replaced every 2-3 years. SCR systems are sensitive to
contaminations & as catalyst has pores they may be plugged by various contaminants
present in untreated gas.

Non-Selective Catalytic Reduction (NSCR):

Simple reducing agents such as H2 or CH4 are used. Besides NOx, oxygen present is
converted .The process is called ‘Non selective catalytic reduction’ because fuel first
depletes all the free O2 present in the tail gas and then removes the NOx & N2O.

2NO+2H2+O2N2+CO2+2H2O

Mostly fuels are natural gas, hydrogen, or ammonia plant purge gas. Catalyst for NSCR
usually based on Pt, V2O5, Iron Oxide. Catalyst supports are made of alumina pellets or a
ceramic honey comb substrate.

Advantages:

NSCR can be used in both new & existing nitric acid plant operating at any pressure. It
results in 95% reduction of N2O emission & also reduces NOx emission. Additionally, heat
generated by operating an NSCR unit can be recovered in a waste heat boiler and a tail-gas
expander to supply the energy for process compression with additional steam for export.

Disadvantages:

Tail gas must be pre heated to start the reaction & high temperature equipment are also
needed.

Comparison for SCR & NSCR:

Characteristic SCR NSCR

Temperature (K) 420 - 670 970 – 1120
Reducing agent NH3 / Urea H2, CH4, Naphtha
Reaction of O2 No Yes
Removal efficiency 85 – 95 % ~90 %

Alkaline absorption:

NOx can be converted to useful products (NaNO2& NaNO3) by scrubbing it with alkali.

With Soda Ash:

Na2CO3 + 2NO2 NaNO3+NaNO2+CO2

Na2CO3+NO+NO2 2NaNO2+H2O
With Caustic Soda:

2NaOH+2NO2 NaNO3+NaNO2+H2O

2NaOH+NO2+NO  2NaNO2+H2O

After concentration, fractional crystallization and subsequent separation of NaNO 2 crystals,

required quantity of Mother Liquor is neutralized with nitrous gases according to the
following reaction: -

NaNO2 + NO2 = NaNO3 + NO

NaNO3 solution is evaporated, crystallized and the crystals are separated. In this NOx
emissions are reduced but N2O is unaffected.

Scrubbing with hydrogen peroxides:

Though the conventional gas scrubbing process with NaOH as conventional scrubbing
medium is good, but the absorbed NOx is converted to nitrite and nitrate which may
present wastewater disposal problems.

What hydrogen peroxide (H2O2) does is that it adds NO contaminants to the scrubbing
solution and allows commercial products to be recovered from the process.

3NO2+H2O  2HNO3 + NO

2NO+HNO3 + H2O 3HNO2

HNO2+H2O2 HNO3+H2O

H2O2 (0.5-1wt. %) and nitric acid (35 - 45wt. %) are used to scrub both NO & NO2. Reactions
are rapid at moderate temperature (30-80°C).

Other methods for abatement of N2O:

There are 3 basic approaches to controlling emissions of N2O from HNO3 plant.

1. Primary control: It involves prevention of N2O from forming .It involves redesigning
nitric acid catalyst gauzes to produce less N2O at source. By this method, it is now
possible to limit N2O concentration to 400 ppm but as catalyst gauzes ages, HNO
formation tends to increase. Hence primary control is not sufficient to meet target
but it improves conversion efficiency
2. Secondary Control: It involves decomposing N2O in the high temperature zone of
pant, immediately after ammonia oxidation catalyst.
3. Tertiary control: It involves decomposing N2O in the tail gas leaving absorber. It has
reached the stage of development where it can reliably attain the desired reduction
in nitrous oxide levels, particularly if used with a low N2O catalyst gauze pack, but it
entails adding dedicated equipment &revising the tail as re heat requirements.
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