REDUCING STACK EMISSIONS FROM AN EXISTING DAP PLANT

David Ivell Director of Process Technology

Van Nguyen Senior Process Engineer
Nitin M Kantak Chief General Manager,
Operations, Zuari Agro Chemicals Ltd

3149 Winter Lake Road, Lakeland, FL 33803

P.O. Box 2008, Lakeland, FL 33806-2008

Prepared for

American Institute of Chemical Engineers

Central Florida Section
4798 S. Florida Avenue, #253
Clearwater Conference

June 6-7, 2014

David.Ivell@jacobs.com Van.Nguyen@jacobs.com
Abstract

Zuari Agro Chemicals Ltd operates a fertilizer complex comprising Ammonia, Urea and
two DAP/NPK Plants at their site in Goa, India. One of the DAP/NPK plants was started
up in December 1984 with a nameplate capacity of 500 t/d. The plant was subsequently
revamped in 1998 to 1100 t/d. The new configuration included a pipe reactor installed in
the dryer. Following the revamp and further in-house improvements, the plant can now
achieve 1300-1400 t/d DAP and 1500-1600 t/d NPK. However, ammonia stack emissions
are high (up to 500 mg/Nm3 with DAP at high production rates).

A study carried out by Jacobs determined that the emissions could be brought down to 35
mg/Nm3 by modifications to the scrubbing system. In broad terms, the recommendation
was to modify the existing, single stage, high mole ratio (1.3-1.4) set up, to a dual mole
ratio arrangement.

Following the study, Jacobs were awarded a contract for basic engineering. This paper
describes in detail the modifications that will be made as well as the challenges faced in
incorporating new equipment in an existing facility with limited space.

1
Zuari Agro Chemicals

Zuari Agro Chemicals Limited operates a fertilizer complex at Goa, India comprising of a
660 MTPD capacity Ammonia Plant, 1140 MTPD capacity Urea Plant, two 1100 MTPD
capacity NPK Plants (NPK-A & NPK-B) and associated Water Treatment, Steam
Generation, Power Generation, Raw Materials & Product Handling and Storage facilities.
The Ammonia, Urea and NPK-A plants were designed, erected and commissioned by
Toyo Engineering Corporation, Japan in 1973. The NPK-B plant with original capacity of
500 MTPD was designed, erected and commissioned by M/s Hindustan Dorr-Oliver Ltd.
(HDO), in December 1984.

Background to the Project

The NPK-B plant was revamped in 1998 to a nameplate capacity of 1100 MT/d. The
engineering was carried out by HDO based on pipe reactor technology from M/s Grande
Paroise, France. The new configuration included a pipe reactor installed in the dryer
along with an Air Chilling system to debottleneck the Product Cooling system. No
modifications were carried out either in the Recycle system (240 MT/hr capacity) or in
the Fume/Dryer Scrubbing system. Following the revamp and further in-house
improvements, the plant can now achieve 1300-1400 MT/d DAP and 1500-1600 MT/d
NPK. However, ammonia stack emissions are high (up to 500 mg/Nm3 with DAP at high
production rates).

Zuari wished to bring the stack emissions down to international norms and launched
RFQ’s to various engineering companies for a study to determine what needed to be done
to achieve these aims. Following an evaluation of the bids, Zuari selected Jacobs to carry
out the study. The contract was awarded in March, 2012.

Study Phase

The study was carried out by the Jacobs, Lakeland office with local support from the
Jacobs, Mumbai office. The objective of the study was to determine the required
modifications to meet the following emissions:

Ammonia............... <35 mg/Nm3

Particulate............. <100 mg/Nm3
Fluoride................. <5 mg/Nm3

2
Preliminary Office Based Assessment

Before embarking on the site visit, a preliminary assessment of the plant in its current
configuration was carried out in Lakeland. Zuari made the following information
available to the study team:

1. Operating Data (operator logsheets, analytical results, etc.)

2. Process Flow Diagrams
3. P&I Diagrams
4. Existing Equipment Specifications
5. General Arrangement Drawings (Layouts) from the original 1980’s design for the
ISBL plant.
6. Surveys over the ventilation systems for airflow, ammonia and particulate
concentrations and static pressures.

Existing Scrubbing System

A simplified flowsheet of the scrubbing system as it was at the time of the study is shown
in Figure 1 below.

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 Figure 1

TAIL GAS COOLER FROM DRYER CYCLONES

SCRUBBER SCRUBBER
PN & GRANULATOR
FUMES FROM DUST CYCLONES
FUME DRYER
FAN FAN

TAIL GAS
SCRUBBER H2O
SUMP
H2SO4

FUME
SCRUBBER
STRONG P2O5 COOLER
DRYER DUST
SCRUBBER
SCRUBBER SCRUBBER
SUMP

FUME DUST
SCRUBBER SUMP SCRUBBER SCRUBBER SUMP
EFFLUENT
TANK
TO PN

The airstreams from the Reactor/Granulator, Dryer and Equipment Dedust Systems are
each scrubbed in separate venturi/cyclonic scrubbers. The scrubbing liquid is circulated
from a common tank, which is fed with phosphoric acid and scrubber water blow-down
from the cooler scrubber, to each of the scrubbers. The scrubber liquor from each
scrubber returns to the tank by gravity via launders.

The data provided showed that the efficiency of each of these scrubbers was very low. It
was determined that the reasons for the low efficiencies were primarily two-fold:

1. The mole ratio in the scrubber tank was maintained at a high mole ratio of 1.3-1.4.
The partial pressure of ammonia above ammonium phosphate at this mole ratio
and operating temperature is approximately 40 times what it is at 0.7 mole ratio
for example. Refer to Figure 2 below.
2. The circulation rates around the scrubbers were very low compared with Jacobs
and industry standards.

4
Figure 2

0.6

0.5
Ammonia Vapor Pressure, mm Hg

0.4

0.3

0.2

0.1

0
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6

N:P Mole Ratio

The scrubber operating conditions are summarized in Table 1 below:

Table 1
Fume Dryer Dust Scrubber Tail Gas
. Scrubber Scrubber Scrubber Tank Scrubber
Mole Ratio - - - 1.3 - 1.4 -
Density, kg/m3 - - - 1350 -
Temperature, °C - - - 49 - 60 -
Liquor Circulation,
m3/h 138 180 90 - 120
Airflow, Am3/h 72,000 129,000 51,000 - 178,600
L/G Ratio, m3/1000m3 1.92 1.39 1.76 - 0.67
Pressure Drop, mm WC 190 300 300 - 75
Efficiency, % 69 80 87 - 70

Dual Mole Ratio Scrubbing

The main conclusion from the review of this data was that a reduction of the stack losses
to the required norms would only be possible if the scrubbing system was to be operated

5
at a mole ratio below 1.0 to minimize ammonia losses due to vapor pressure. However, in
order to limit fluoride stripping in the scrubbing system, it was decided that conversion of
the scrubbing system from a single mole ratio operation to a dual mole ratio configuration
would be advantageous. Refer to Figure 3 below, which demonstrates the effect of mole
ratio on fluoride emissions.

Figure 3

180

160

140

120
Fluorine, mg/m3

100

80

60

40

20

0
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6

N:P Mole Ratio

In addition to this advantage, scrubbing efficiency is obviously increased due to the

installation of additional scrubbing stage in series.

Water Scrubbers

The tail gas scrubber and the cooler scrubber use water as the scrubbing medium. Both
scrubbers are simple void towers with a series of spray nozzles. Water is fed to the tail
gas scrubber as make up and this in turn is blown down and used as make up in the cooler
scrubber. Finally the blow-down from the cooler scrubber is fed forward to the scrubber
effluent tank to control the density of the circulating acid.

The study determined that these two scrubbers were also not very efficient. It was
concluded that the circulation rates were again very low compared with Jacobs and

6
industry standards. In addition, it was concluded that in order to ensure that the target
emissions were met; packing should be installed in the tail gas scrubber.

Dryer Pipe Reactor

The dryer pipe reactor operates at a mole ratio of approximately 1.0. It is fed with strong,
merchant grade phosphoric acid and liquid ammonia. About 50% of the P2O5 is fed via
this pipe reactor. Based on several old papers describing this technology, we had
expected that the MAP produced in this pipe reactor would be recycled back to the
granulator, either as cyclone dust or as fines from the screens.

If this was the case, the recycled MAP would be ammoniated to DAP in the granulator,
meaning that considerably more ammoniation would be required beneath the bed than is
the case in a conventional process and therefore losses of ammonia in the granulator
exhaust would be very large.

However, in practice it was found that the MAP from the pipe reactor actually appears to
coat the surface of the granules as they are cascading in the dryer. The good news is that
the degree of ammoniation in the granulator and the losses in the granulator exhaust are
not nearly as bad as had been anticipated. However, the bad news is that the MAP
reduces the mole ratio of the product considerably. This means that even though the
feedstock to the plant is relatively pure merchant grade acid from Morocco, urea is
required to achieve 18% nitrogen in the product.

Regardless, no changes were proposed to this system at this point.

In summary, the plan for the modified system was as follows:

1. Re-configure the existing Fume Scrubber for use as the Pre-scrubber, operating at
high mole ratio (1.4-1.5).
a. Remove the existing venturi and replace with a simple duct scrubber.
b. Re-use the existing cyclonic separator.
c. Remove sprays from the body of the cyclonic separator and relocate to the
throat of the cyclonic inlet.
d. Add an integral sump to the bottom of the existing cyclonic separator.
e. Install new high circulation pumps to circulate scrubber liquor to the duct
scrubber sprays and pump the blow-down to the preneutralizer.
f. Re-direct the gases from the cyclonic separator to a new venturi/cyclonic
scrubber.
2. Install a new venturi/cyclonic scrubber, operating at low mole ratio (0.6-0.7).
a. Jacobs design with variable throat and sprays directed into the throat.
b. Install new high circulation pumps.
c. Direct the gases from the cyclonic separator to a new fan designed for a
higher pressure.
3. Re-utilize the existing tail gas scrubber.
a. Install packing to improve efficiency

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 b. Install new high circulation pumps
c. Install a mixing tee in the scrubber circulation line to enable pH to be
controlled at 4-5 to improve ammonia recovery.
4. Install new dryer fan
a. Designed for higher pressure due to the packing in the tail gas scrubber

The revised flowsheet is shown below in Figure 4.

Figure 4

H2SO4

FROM DRYER
COOLER CYCLONES
SCRUBBER
TAIL GAS FROM DUST
SCRUBBER CYCLONES
PN & GRANULATOR FUME DRYER
FUMES FAN FAN

TAIL GAS
SCRUBBER
SUMP H2O

COOLER
PRE- FUME SCRUBBER
SCRUBBER SCRUBBER SUMP
DRYER DUST
TO PN SCRUBBER SCRUBBER

STRONG P2O5

DUST
SCRUBBER SCRUBBER SUMP
EFFLUENT
TANK

8
The design conditions in the new system are summarized in Table 2 below:

Table 2
Pre- Fume Dryer Dust Scrubber Tail Gas
. Scrubber Scrubber Scrubber Scrubber Tank Scrubber
Mole Ratio 1.5 - - - 0.7 -
Density, kg/m3 1300 - - - 1280 -
Temperature, °C 75 - 80 - - - 55 - 60 -
Liquor Circulation,
m3/h 195 140 245 95 - 450
Airflow, Am3/h 73,000 73,000 129,000 51,000 - 210,000
L/G Ratio, m3/1000m3 2.67 1.92 1.90 1.86 - 2.14
Pressure Drop, mm WC 175 450 300 300 - 185
Efficiency, % 68 95 80 87 - 95

Site Visit

The site visit took place on April 25, 2012. Having determined in principle what was
required to reduce the stack losses to the required values, the main focus of the site visit
was to determine how this could be achieved in practice.

It quickly became apparent to the study team that this was not going to be an easy task.
Since the plant had been built, the entire scrubbing system had been enclosed in a new
building with siding and a roof. Space inside the building was at an absolute premium.
No space could be found within the existing scrubber building for the new scrubbing
stage.

Fortunately, adequate space was identified just to the south of the scrubber building. In
order to accommodate the new scrubber and fan however, an existing solid intake system
for potash would have to be relocated as the new scrubber structure would partially
overlap. Space was identified for the new circulation pumps adjacent to the existing
scrubber tank. However, due to the distance between the new scrubber and the existing
tank, it was not a practical possibility for the liquor return to be accomplished by gravity
via a launder. Therefore, new pumps located adjacent to the new scrubber, will be
installed to pump liquor back to the tank.

The cyclonic separator, which was to be re-used for the pre-scrubber, had body flanges
for the cyclonic inlet, conical liquor outlet and on the main body close to the gas outlet.
This made the necessary changes easier to accomplish than might have been the case
otherwise.

The new duct scrubber could simply be flanged up to the existing cyclonic inlet. New
sprays will be installed to spray into the inlet.

9
The existing shallow conical liquor outlet will be replaced by a much larger integral sump
as sufficient residence time is required to allow for stable mole ratio control in the pre-
scrubber. The existing body flange will be used. The complication that was identified was
that the new integral sump fouls with the existing structure and will have to be re-worked
during detailed engineering. Space was identified at grade for the new pre-scrubber
circulation pumps.

By unbolting the main body flange at the top of the cyclonic outlet and re-directing it, it
was possible to run the exhaust duct in a straight shot over to the new Fume Scrubber.
The new duct run doesn’t interfere with any of the existing structural steel of the
building.

The new fume fan will be located outside the existing scrubber building and will be
located at grade within the new Fume Scrubber structure. The new dryer fan will
however basically occupy the same space as the old fan.

The report, which included an order of magnitude estimate carried out by the Mumbai
office, was finalized and issued in June 2012.

A plan view of the revised system is shown below in Figure 5.

10
Figure 5

11
A side view looking west of the revised system is shown below in Figure 6.

Figure 6

Basic Engineering Phase

Funding for the project was not made available until 2013. On August 28, 2013, Jacobs
was awarded a contract to prepare a basic engineering package based on the study that
was completed the previous year. The package was completed in March, 2014.

Deliverables were prepared for the conversion of the single mole scrubbing system to a
dual mole system as described below.

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The existing Fume Scrubber will be modified for use as the Pre-Scrubber (High Mole
Ratio scrubber). As the scrubber will operate at high mole ratio (approximately 1.5) the
efficiency will only be around 60-70% due to the ammonia vapor pressure. A high
pressure loss venturi is therefore not warranted.

The venturi will be replaced with a simple duct and sprays. The existing scrubber liquor
line and associated branches will be removed along with the venturi. The cyclonic
separator will be retained. However, the sprays that are currently located in the cyclonic
separator will be removed and replaced with a spray located in the inlet duct to the
cyclonic separator.

Gases from the Pre-neutralizer and Granulator will flow through existing duct and enter
the modified Pre-Scrubber at the same elevation. The bottom cone of the cyclonic
separator along with down leg will be removed and replaced with an integral sump.

Structural clearance is required to extend the cyclonic separator and therefore; the
existing Fume Scrubber Sump, connected launder, and associated piping will be
removed. Phosphoric acid currently fed into the Fume Scrubber Sump will be rerouted to
the Scrubber Effluent Tank.

Two (2) new Pre-scrubber Pumps (one operating and the other standby) will be provided
to circulate scrubber liquor through the Pre-scrubber sprays and to feed the Pre-
Neutralizer.

The Pre-scrubber will be fitted with a new nozzle for a phosphoric acid feed for the
purpose of start-up, product grade changes, and mole ratio correction.

The top portion of the cyclonic separator will be rotated at the body flange to redirect the
outlet towards the location of the new Fumes Scrubber which will be located to the south
outside the scrubber area building.

A new venturi-cyclonic Fume Scrubber of Jacobs design will be provided. The Fumes
Scrubber will have sprays located above the venturi and also in the inlet duct to the
cyclonic section. The venturi will have a variable throat to control the pressure drop at
400 mm WC.

New Fume Scrubber Pumps will be provided in place of existing Scrubber Effluent
Pumps to pump scrubber liquor from the existing Scrubber Effluent Tank to the new
Fume Scrubber and Pre-Scrubber. The cyclonic separator will have an integral sump.

New Fume Scrubber Return Pumps equipped with VFD will be provided to pump
scrubber liquor from the integral sump back to the Scrubber Effluent Tank. In the new
configuration, the Scrubber Effluent Tank will operate at low mole ratio (approximately
0.7).

13
Neither the Dryer Scrubber nor the Dust Scrubber will be modified. However, the
existing Scrubber Liquor Pumps will now feed only these two scrubbers. Since the Fumes
Scrubber will have its own dedicated pumps, line from Scrubber Liquor Pumps to
existing Fume Scrubber will be removed. This will allow the circulation rate around these
scrubbers to be increased to the standard of approximately 2m3/1000m3 of airflow with
the corresponding increase in scrubber efficiency.

The existing Tail Gas Scrubber is a square section void tower with a very low circulation
rate. Efficiency is very low (approximately 70%) despite scrubber water pH being
controlled between 3 and 5.

Jacobs evaluated several options for obtaining scrubbing efficiency, all of which imposed
greater weight and liquid loads on the existing unit and decided upon a fluidized bed
scrubber containing beds of low density spheres. These spheres are free to fluidize
between internal upper and lower retaining grids. Liquid is introduced by way of spray
headers at the top of the scrubber and travels downward while the gas to be reacted
travels upward, countercurrent to the liquid flow. Gas velocities and liquid flow rates are
maintained so that the sphere bed fluidizes in the gas stream. The fluidization permits
high flow rates of both gas and liquid through the scrubber. These high flow rates result
in mass and heat transfer rates far in excess of those possible in conventional stationary
packed designs. The fluidizing action is also self-cleaning to some extent.

An initial field survey, at the start of the basic engineering phase, raised questions about
the mechanical condition of the Tail Gas Scrubber and its rubber lining. Zuari arranged
for an internal and external inspection report during a planned plant outage. The report
detailed overall poor condition of the rubber lining that required significant repairs. In
addition, the carbon steel shell was badly corroded in multiple areas and in some places,
completely corroded through. The repairs would have to be carried out in-situ and the
plant shutdown until the work was complete. In order to avoid the long downtime, Jacobs
recommended a new Tail Gas Scrubber. Multiple options were studied, including
replacement in kind and replacement with a circular cross-section vessel in either rubber
lined carbon steel or stainless steel. In the end, Jacobs recommended a new circular cross-
section, stainless steel vessel. The vessel will be fabricated either in the shop or on-site,
and the plant can continue to operate while the new vessel is being fabricated. The
downtime will be significantly reduced as all that is required is for the existing vessel to
be removed, the new vessel installed in its place and hooked up (duct and pipe). When
the construction is complete, the new Tail Gas Scrubber will not have any of the
maintenance problems associated with rubber lining.

Zuari accepted the proposal of a new stainless steel cylindrical tower, specified with two
beds of fluidized packing.

The existing Cooler & Tail Gas Scrubber Circulation Pumps will be replaced to meet the
new capacity for the higher L/G ratio in the Tail Gas Scrubber. Zuari requested the
evaluation of existing Wilfley AF 225-540 pumps residing on site for this application. It

14
was determined that the Wilfley pumps could be reused but modified with a new belt
drive and new motor for the increased capacity.

pH in the Cooler Gas Scrubber and Tail Gas Scrubber is currently adjusted by the
addition of sulfuric acid to the Cooler Gas Scrubber Sump. The Cooler Gas Scrubber
Sump is suffering from corrosion. Therefore, a new mixing tee will be provided in the
circulation line to the Tail Gas Scrubber to inject small amounts of Sulfuric acid into
large flow of scrubber liquor. The current Sulfuric acid supply line to the Cooler Gas
Scrubber Sump will be removed.

On-line pH measurement will be provided. pH will automatically be controlled by

adjusting the flow of sulfuric acid to the mixing tee. Temperature indication will be
provided on Tail Gas Scrubber Sump to close sulfuric acid valve feed to the mixing tee
on high-high temperature.

A new Fumes Fan will be required to allow for the higher pressure drop of the new
Fumes Scrubber and the Tail Gas Scrubber packing. The new Fumes Fan will be located
outside the existing scrubber building directly to the south of the existing fan. The new
Fumes Fan will discharge into the existing inlet nozzle feeding the Tail Gas Scrubber.

A new Dryer Fan will be required to overcome the additional pressure drop across the
venturi resulting from the increased liquor circulation and the additional pressure drop
across the Tail Gas Scrubber resulting from the packing.

Future Plans for the Project

The implementation of the Project would take about a year. The detail engineering,
procurement and construction of the project are planned as per the following schedule.

Activity Duration, Months Start/End Date

Detail Engineering 4 Mid Jun-14 / Mid Oct-14
Procurement 10 Jul-14 / Apr-15
GA Drawings Release - Oct-14
Civil Work 6 Nov-14 / Apr-15
Erection of Equipment 5 Jan-15 / May-15
Hook-ups/Commissioning 0.6 Mid May-15 / Jun-15

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Detail Engineering

Zuari is in discussions with the Jacobs, Mumbai office for the detail engineering of the
project. The order is expected to be finalized by mid June, 2014. The detail engineering is
expected to be completed by October 2014, by which time the general arrangement
drawings will be released for civil construction.

The major challenges expected for the implementation of the project are:

 Civil construction/installation of new Jacobs design fume scrubber and fumes fan
at a new location south of the tail gas scrubber, which partly fouls with the
existing Potash feed belt. This will have to be relocated to carry out the
installation of fume scrubber/fan.
 Modification of existing fume scrubber to pre-scrubber by replacement of venturi
with duct scrubber, replacement of bottom cone of cyclonic separator/down
comer with integral sump and re-orientation of cyclonic separator gas outlet in the
direction of new fume scrubber.
 Replacement of square cross section Tail Gas scrubber with new conical scrubber.
 Replacement of dryer fan at existing location, possibly with minor modification of
the existing foundation.

Zuari will work with the Jacobs, Mumbai office to minimize the shutdown required to
meet above challenges.

Construction Methodology

The main objective during construction would be to minimize the shutdown time. A list
of all activities is being prepared. This list will be segregated into three groups: Pre-
Shutdown activities, Planned Short Shutdown activities and Planned Long Shutdown
activities.

Pre-Shutdown activities

We plan to carry out following activities while the plant is in operation:

 Civil construction/installation of new Fumes scrubber/Fumes Fan

 Foundation for Pre-scrubber (modified existing fume scrubber)
 Foundation for Pumps/Installation of pumps at new locations.
 Pre-fabrication of piping /ducting.
 Laying of electrical/instrument cables wherever possible.
 Installation of DCS system.
 Installation of 3.3 KV MCC for Fumes Fan (existing 440V MCC)

16
Planned Short Shutdown activities

Re-routing of ducting/piping/cabling wherever fouling with new equipment, would be

completed in short 1-2 day shutdowns.

Planned Long shutdown activities

A long shutdown of about two weeks towards end of May, 2015 is planned for final hook
up. The following major activities will be planned:
 Pre-scrubber Installation (Removal of venturi /Installation of Duct scrubber,
modification of conical liquor outlet, re-orientation of gas outlet).
 Removal of existing Tail Gas scrubber/ Installation of new tail Gas scrubber.
 Installation of new Dryer fan on existing/modified foundation.
 Final hook up of ducting / piping / cabling.
 Hook up of DCS system/Electrical system.
 Pre-commissioning and Commissioning.

Conclusion

Zuari's revamped NPK-B plant's current ammonia stack emissions is in the order of 500
mg/Nm3. Jacobs was solicited to perform a study to review the existing plant and
determine the necessary modifications to reduce the losses to less than 35 mg/Nm3.

The Jacobs Lakeland and Mumbai offices performed the study to define the necessary
design that will convert the current plant operation to a dual mole ratio mode and achieve
the level of emission that is required.

When funding become available, the Jacobs Lakeland office was able to move forward to
deliver a basic engineering package to implement the design as outlined in the study.

The Jacobs Mumbai office will carry out the detail engineering to meet Zuari's plan of
start-up in June, 2015.

The project is a good example of the Jacobs stage-gated process (JSTEPS):

Phase 1; Opportunity Analysis. Carried out by Zuari.

Phase 2; Conceptual Design. Carried out by a combined Jacobs Lakeland and Mumbai
team.

Phase 3; Project Definition. Production of a Basic Engineering Package by the Jacobs

Lakeland office.

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Phase 4; Detailed Design. Will be carried out by the Jacobs Mumbai office with support
from Lakeland.

The project is also a good example of Jacobs multi-office execution involving both the
Lakeland and Mumbai offices. Full advantage was taken of the local presence in India to
provide an efficient and cost effective project execution approach that provided value to
the client.

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