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2. Process Description
Fertilizers industry is a form of secondary chemical production. It is
necessary to understand the inputs and processing techniques in order to
identify the pollution sources and abatement measures in this industry.
Fertilizers may be categorized into two groups, natural and synthetic
fertilizers. Synthetic fertilizers include different types according to their
chemical composition, physical status and solubility in water. According
to their chemical composition, fertilizers are categorized into three main
groups as follows:
Phosphatic fertilizers containing phosphorous as a base element,
which is epressed by P
!
"
#
$.
%itrogen fertilizers containing nitrogen as a base element, which
is epressed by %
!
$.
Potassium fertilizers containing potassium as a base element,
which is epressed by &
!
" $.
In addition to the straight fertilizers containing single nutrient '% or P or
&( there are the comple fertilizers containing two or three ma)or plant
nutrient %.P.&. *normous +arieties of %P& according to their contents
of nutrients are a+ailable. ,iquid fertilizers are also produced worldwide
including hundreds of forms containing one or more nutrients together
with trace elements. %P& fertilizers are produced in the *gyptian
Fertilizer -e+elopment .enter Pilot Plant, located in /al0ha, in limited
quantities according to the clients requests. Also in -elta .ompany there
is a plant that produces urea1 ammonium nitrate liquid fertilizer '2! $
%(.
/he liquid fertilizers must be free of solids to a+oid clogging the slurry
nozzles. .oncentrated phosphoric acid is used as the basis for high
analysis liquids. 3hen reacted with ammonia, it gi+es neutral solution
which does not crystallize at low temperature. If ammoniated under
pressure, ammonium polyphosphate forms. /his can be stored and
shipped as a solid and dissol+ed readily when needed. Another liquid
fertilizer is anhydrous ammonia, +aporized to a gas and ploughed
directly into the soil. A combination of solution4 suspension containing
52 $ nitrogen and 62 $ P
!
"
#
has been de+eloped, to which custom
blenders can add potash and trace elements if needed.
Raw Materials, Chemicals and Other Inputs
Main Raw Materials
Inputs for the fertilizers industry +ary according to the fertilizer type.
Phosphate roc0 is considered the main raw material for the production
of phosphate type fertilizers, while in case of nitrogenous fertilizers,
ammonia is considered the main raw material. Ammonia is produced by
synthesis of nitrogen and hydrogen. /he latter is generated either by
steam reforming of natural gas, or electrolysis of water. "n the other
Environics July 2002
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Inspection Manual for Fertilizers Industry
hand, nitrogen is produced either from air liquification as in &I7A1
Aswan, or combustion of natural gas.
,arge quantities of acids are also used, namely sulphuric acid, nitric acid
and phosphoric acid. In all fertilizers plants those acids are produced on1
site. 8aw sulphur is considered the main raw material for the production
of sulphuric acid, whereas phosphoric acid production depends on
phosphate roc0 as raw material. /he production of nitric acid is based on
the on1site produced ammonia.
/he in+ol+ed catalysts in the fertilizers industry are as follows:
In ammonia production:
.o", 7o"
2
and 9n" for sulphur remo+al.
%i" for primary and secondary reformers.
Iron oide and chromium for ." high shift con+ersion
and copper oide and zinc oide for low shift.
%i" catalyst for methanation.
Iron promoted catalyst for ammonia synthesis.
In nitric acid production: platinum4 rhodium catalyst.
In sulphuric acid production: +anadium pentoide catalyst.
/hese catalysts are usually not considered as inputs, instead they are
considered part of the equipments. /his is related to nature of the
reactors in this industry, which are fied bed reactors. :ence the
catalysts only aid the reaction, without reacting themsel+es. According
to se+eral factors, catalysts loose their acti+ity after long operating hours
which defer from a catalyst to another. .onsequently, they need to be
regenerated, usually on1site ecept for the +ery epensi+e catalysts such
as platinum alloy catalyst which is regenerated in the manufacturing
company.
Sol+ents, carbon dioide, ground dolomite as coating materials and
limestone are also used in fertilizers industry. /able '!( summarizes the
ma)or inputs according to the in+ol+ed operation.
Other Inputs (Water, Fuel and Steam
,arge quantities of water are consumed for se+eral purposes in+ol+ing
cooling, process, steam generating, floor washing and cleaning, ..etc.
Steam is generated in these plants in huge quantities for heating,
reforming, stripping and other purposes. /his steam is generated in
boilers by fuel combustion. /he fuel type differs from one facility to the
other, including fuel oil 'mazot(, gas oil 'solar( or natural gas. Fuel oil
'mazot( is widely used due to its cheap cost. "n burning, it generates on
burning air emissions with high concentration of sulphur oides 'S"
(.
Air is also necessary for some operations such as drying and cooling.
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Inspection Manual for Fertilizers Industry
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Inspection Manual for Fertilizers Industry
!a"le (2 !he Main Inputs in Fertili#ers Industr$
Production Processes
Fertilizers industry is considered one of the comple chemical sector,
which includes se+eral production lines and ser+ice units. /hese are
gi+en in table '2(.
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Operation Inputs
Single superphosphate roduction
Acidulation - Phosphate roc0
- Strong sulphuric acid
- 3ater
-rying - Air
;agging - Polyethylene bags
!riple Superphosphate roduction
8eaction - <round phosphate roc0
- Phosphoric acid
-rying - :ot air
;agging - Polyethylene bags
hosphoric "cid roduction
3ashing - <round phosphate roc0
- 3ea0 phosphoric acid
8eaction - Sulphuric acid
Sulphuric "cid
7elting - Sulphur
-rying of air - Sulphuric acid '=> $(
Absorption - -iluted sulphuric acid
Synthetic "##onia roduction
-esulphurization - %atural gas
- Adsorbent
Primary reforming - Steam
Secondary reforming - .ompressed hot Air
."
!
separation - Sol+ent mono1ethanol amine or potassium
carbonate and other sol+ents
$itric "cid
Filtration - Air
?aporization - Ammonia
"idation - <aseous %:
2
- Air
%o
and air
compressors.
Air pollution and contamination from the ammonia can poison
the catalyst. /his effect, as well as poor ammonia1air miing and
poor gas distribution across the catalyst, may reduce the yield by
5C $. 7aintenance of the catalyst operating temperature is +ery
important for the %" yield. /his is achie+ed by ad)usting the
air4ammonia ratio and ensuring that the lower eplosi+e limit for
ammonia in air is not eceeded. /he preheated ammonia is
thoroughly mied with preheated air and sub)ected to further
filtration to a+oid contaminants from entering to the catalyst.
/he ratio of ammonia air miture is controlled by a high
precision ratio controller which is considered as the safeguard
for protecting arising from:
.atalyst temperature eceeds >#C
o
.
Ammonia4 air ratio eceeds 5!.# $ 'in atmospheric
oidation( or 5C $ 'in case of pressure oidation(
Failure of air compressor or %o
compressor Netc
/he water produced in oidation is then condensed in a cooler1
condenser and transferred to the absorption column. %itric oide
is oidized to nitrogen dioide as the combustion gases are
cooled. For this purpose secondary air is added to the gas
miture obtained from the ammonia oidation to increase the
oygen content to such a le+el that the waste gas lea+ing the
plant has a normal oygen content of between ! 1 6 $.
65 Energy 7ecovery
/he hot reaction gases are used to produce steam and4or to
preheat the waste gas 'tail gas(. /he heated waste gas is
discharged to the atmosphere through a gas turbine for energy
reco+ery. /he combustion gas after this heat transfer for energy
reco+ery, has a temperature of 5CC to !CC
o
., depending on the
process and it is then further cooled with water.
'5 &ooling
*it gases '%", ecess air and water +apour( are cooled
through a water cooler in two stages, where nitrogen oides are
then dissol+ed in the water condensate to form a +ery diluted
nitric acid 'about !$ conc.( which is collected in a tan0. /he
Environics July 2002
2*
Inspection Manual for Fertilizers Industry
collected diluted acid is withdrawn by pumps and discharged to
the bottom of the absorption tower. /he remaining gases are
withdrawn, together with ecess air, by compressing turbines to
the absorption towers.
)5 "-sorption1
/he absorber is operated with a counter1current flow of
water. the absorption of the nitrogen dioide and its
reaction to nitric acid and nitric oide ta0e place
simultaneously in the gaseous and liquid phases. /he
main reaction ta0ing place is as follows:
!%" D "
!
F !%"
!
2%"
!
D :
!
" F !:%"
2
D %"
!%"
!
F %
!
"
6
/hese reactions depend on pressure and temperature to a
large etent and are fa+ored by higher pressure and lower
temperature.
Series of towers with 2.#m diameter and !6m height are
used in this stage. /he absorber1reactor is a sie+e plate or
bubble cap unit with cooling coils on each of the !C to #C
trays. <as enters at the bottom, dilute nitric acid part way
up the column, with cold water entering at the top. In the
first tower most of the oidation operation ta0es place
where %" is con+erted to nitrogen dioide. -iluted
%itric acid is then formed, collected in a le+el tan0 and
discharged to the bleaching operation. .hlorine
impurities presents a unique problem in the absorber,
they cannot be transferred through the bottom neither can
they lea+e in the top gas. /herefore, they must be
ecluded from entry or pro+ision made for their purging
as the reaction of nitric oide proceeds during gas flow.
.onsequently the gases are cooled 'remo+e heat of
reaction and promote oidation reactions to go to
completion(, against the cold tail gases coming out of the
absorption tower to preheat them before entering the tail
gas turbine. /he preheated tail gas passes through the
epansion turbine 'part of the %"
compressor dri+es( to
reco+er the energy and reduce tail gas temperature. /hen
further cooled before passing through the series of
counter1current pac0ed towers.
*5 8leaching
/he acid lea+ing the bottom of the column contains some
%"
, mostly as %
!
"
6
'colorless( but some as red %"
!
. It
is therefore sent to a bleaching tower to eliminate its
colour. In bleaching operation the acid is sprayed at the
top of the tower 'about #.#m height and =C cm diameter(,
which is filled with a 8aschig rings at the bottom. A
counter current air stream is introduced at the bottom of
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Inspection Manual for Fertilizers Industry
the tower through a screen, to absorb the gases from the
acid then withdrawn from the top of the tower. /he acid,
free from gases, is collected at the bottom of the tower
and then cooled in cooling plates and sent to storage
tan0s. .ooling plates are essential, especially at the first
tower, where the highest quantity of heat is released
because most of the oidation and absorption reactions
ta0e place in that tower.
Fig '>( illustrates the bloc0 diagram for nitric acid production.
Ma/or 0azards
/he following hazards may arise during nitric acid production:
equipment4piping failure because of corrosion
eplosion hazard due to the air ammonia miture
eplosion of nitrite4nitrate salts.
.orrosion protection is achie+ed by the well pro+en use of
suitable austenitic stainless steel where condensation can occur
and by regular monitoring of conditions. Safety is ensured by the
automatic closure of the ammonia control +al+e and separate
shutdown trip +al+e when too high an air ammonia ratio is
measured, either from each indi+idual flow meter or indirectly
from the catalyst gauze temperature. /he air ammonia ratio
should be continuously controlled and 0ept below the hazardous
range. Any free ammonia present in the nitrous gas will ha+e a
deposit of nitrite4nitrate in a cold spot. ,ocal washing and well
pro+en operating practices will pre+ent the hazard.
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Inspection Manual for Fertilizers Industry
Fi) (8 Process Flow Dia)ram +or 6itric .cid Manu+acturin)
Inputs Operations Outputs
Air
;ac0wash wastewater
Filter ca0e
Spent lube oil
%oise
,iquid Ammonia
Steam
Fugiti+e ammonia
:eat stress
Pt @ rhodium
catalyst
Fugiti+e ammonia, %
!
"
3ashing water of filters
:eat stress
Process 3ater
Fugiti+e ammonia
;lowdown
Filtered @ .ompressed air
.ooling 3ater
.ooling wastewater
recycled to cooling towers
/o epander '%o emissions(
Process water
.ooling water
.ooling wastewater to towers
Acid mist, %o
emissions
Air
46O
%
(00 2 conc.
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,2
Filtration
.ompression
?aporization
%:
2
"idation
.ooling in 3:;
Filtration
.ooling
Secondary
"idation of %itric
"ide
Absorption
;leaching
.ooling by /ail <as
Inspection Manual for Fertilizers Industry
c( Methanol roduction
/his unit replaced the copper liquor 'ammoniacal copper formate
or acetate( section which was used for the remo+al of ." from
synthesis. /he liquor pollutes water streams as it contains
copper, ammonia and carbonic acid. /he copper liquor reacts
with ." which later released when the solution is regenerated.
7ethanol is formed by the reaction of ." and ."
!
with
:
!
according to the reaction:
." D !:
!
F .:
2
":
."
!
D 2:
!
F .:
2
": D :
!
"
/his reaction ta0es place at !5C
o
. and !!C atmosphere in presence of
.u " and 9n" catalyst. /he product is raw methanol which is purified
by distillation to == $ concentration.
Fig '=( shows the process flow diagram for methanol production.
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Inspection Manual for Fertilizers Industry
Fi) (9 Process Flow Dia)ram +or Methanol Production
Inputs Operations Outputs
Synthetic gas
3ater
.atalyst '.u", 9n"(
%:
2
, .", :
!
emissions
:eat stress
Steam
Synthesis gas to
methanator
.", :! emissions
Steam 3astewater '.:
2
":(
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,4
7ethanolation
Separation
-istillation
7ethanol
Storage
Inspection Manual for Fertilizers Industry
d( "##oniu# $itrate roduction
Ammonium %itrate is in the first place a nitrogenous fertilizer
representing. 5!.6$ of the total nitrogen consumption
worldwide. It is more readily a+ailable to crops than urea. In the
second place, due to its powerful oidizing properties is used
with proper additi+es as commercial eplosi+e.
/he production process comprises three main unit operations:
neutralization, e+aporation, solidification 'prilling and
granulation(. Indi+idual plants +ary widely in process detail.
+3 $eutralization1
Anhydrous liquid ammonia is e+aporated in an
e+aporator using cooling water. /he stoichiometic
quantities of nitric acid '##$ concentration wt4 wt( and
gaseous ammonia are introduced by an automatic ratio
controller to a neutralizer. /he reaction between
Ammonia and nitric acid produces ammonium nitrate
solution according to the following eothermic reaction.
%:
2
D :%"
2
%:
6
%"
2
%eutralization can be performed in a single stage or in
two stages. /he neutralizer can be carried out at
atmospheric 'either normal or low emission neutralizers
where the temperature does not eceed 5C#. and p:
will be B and 2 respecti+ely( or at ele+ated pressure of
almost 6 atmospheres. /he normal neutralizers are
usually followed by flash e+aporation in order to in
crease the out let A.% concentration to EC$. In case of
pressure neutralizers the temperature will be in the range
of 5E>. and the steam generated from the heat of
reaction will be utilized in the subsequent step namely
concentration of A.% solution.
-uring e+aporation some ammonia is lost from the
solution. /he steam which is boiled off is contaminated.
/he control of the neutralizer is important. /he p: and
the temperature must both be strictly controlled to limit
the losses from the neutralizer. All installations must
include p: and temperature controls. At the operating
temperature of the neutralizer, impurity control is of great
importance because a safety incident will also be a
significant en+ironmental incident. /he ammonium
nitrate solution from neutralizer may be fed to storage
without further processing but, if it is used in the
manufacture of solid ammonium nitrate, it is concentrated
by e+aporation.
Environics July 2002
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Inspection Manual for Fertilizers Industry
23 Evaporation to &oncentrate the "3$
/he outlet from the neutralizer is recei+ed in an
intermediate tan0. /he solution should be made al0aline
before being pumped 'no need for pumps in case of
pressure neutralizers since the pressure will maintain the
flow( to the e+aporation section 'multi1effect( running
under +acuum. /he solution will be steam heated in the
multi effect e+aporation section. /he solution will be
concentrated up to =E.#1==.#$ 'normally o+er == $(
depending on whether ammonium nitrate will be
granulated or prilled.
,3 Mi4ing the Filling Material1
In order to reduce the nitrogen content of A.% from 2#$
to 22.#$, the proper filling material is added 'about 6$
by weight of powdered limestone or dolomite or e+en
0aolin(
43 rilling or 9ranulation
/he hot concentrated melt is either granulated 'fluidize
bed granulation, drum granulation N etc( or prilled.
Ammonium nitrate is formed into droplets which then fall
down a fall tower 'prill tower( where they cool and
solidify. <ranulation requires more complicated plant
than prilling and +ariety of equipment. /he main
ad+antage of granulation with respect of en+ironment is
that the quantity of air to be treated is much smaller and
abatement equipment is cheaper.
53 :rying; Screening
/he ammonium nitrate 'prills or granules( is dried
'usually in drums( using hot air 'steam heated(, then
screened to separate the correct product size. /he
o+ersize and undersize will be recycled either in the
miing tan0 'in case of prilling( or to the granulator.
63 Final &ooling
/he hot proper size granules, are then cooled 'against
cooled and humid free air( down to 6C. and treated with
anti1ca0ing 'usually amines( and then coated with an inert
material 'usually, 0aolin, limestone or dolomite( and then
con+eyed to the storage.
Fig '5C( illustrates the bloc0 flow diagram for ammonium nitrate
production process.
Ma/or 0azards
Ammonia, nitric acid and ammonium nitrate are the hazardous
chemicals present in ammonium nitrate plants. A.% is an
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,6
Inspection Manual for Fertilizers Industry
oidizing agent and precautions must be ta0en in manufacturing,
transport and storage.
/he main chemical hazards associated with ammonium nitrate
are fire, decomposition and eplosion. ;urns caused by hot A%
solution should also be considered from a safety point of +iew.
Ammonium nitrate itself does not burn. ;eing an oidizing
agent, it can facilitate the initiation of a fire and intensify fires in
combustible materials. :ot A% solution can initiate a fire in rags,
wooden articles ets., on coming into contact with them.
Similarly, fertilizer products or dust contaminated with oil or
other combustible materials can also start fires when left on hot
surfaces.
Pure solid A.% melts at 5B=
o
.. "n further heating it decomposes
by way of a comple series of reactions. Ap to about !#C
o
. it
decomposes primarily into %
!
" and :
!
". Abo+e 2CC
o
. reactions
producing %!, %", %"
!
etc., become significant. /hese
reactions are eothermic and irre+ersible. /hey are accompanied
by the +apour pressure dependent endothermic dissociation into
:%"
2
and %:
2
+apours which can pro+ide a temperature
limiting mechanism, pro+ided the gases can escape freely. If
they cannot, the endothermic dissociation is suppressed and a
run1away decomposition can de+elop, leading to eplosi+e
beha+ior. A number of materials ha+e a strong catalytic effect on
the thermal decomposition of A.%. /hese include acids,
chlorides, organic materials, chromates, dichromate, salts of
manganese, copper and nic0el and certain metals such as zinc,
copper and lead. /he decomposition of A% is suppressed or
pre+ented by an al0aline condition. /hus the addition of
ammonia offers a ma)or safeguard against the decomposition
hazard. /he release of toic fumes is one of the main hazards
associated with the decomposition of A%.
Strongly acidic conditions and the presence of contaminants
should be a+oided to counter the eplosion hazard in A%
solutions. *plosions can occur when ammonium nitrate is
heated under confinement in pumps. 8easons for pump
eplosions include:
5( %o 'or insufficient( flow through the pump.
!( incorrect design 'design may incorporate low flow and4or high
temperature trips(.
2( poor maintenance practices.
6( contamination.
It is more common for the ma)or storage of these chemicals to be
located within their own manufacturing plants. Possible
requirements for storage
materials of construction used in the building of the store,
other buildings in the locality, storage of other product in
the same building, absence of drains, fire detection and
fire fighting systems, layout and size of stac0s
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Inspection Manual for Fertilizers Industry
Fi) (*: Process Flow Dia)ram +or .mmonium 6itrate Manu+acturin)
Inputs Operations Outputs
,iquid Ammonia
%itric Acid
Ammonia
emissions
Steam condensate '%:
2
,
ammonium nitrate(
?apours to ammonium
nitrate separator
Ammonia in)ection
Steam
Steam
?apours to ammonia
separator
.ondensate '%:
2
,
ammonium nitrate(
-olomite, &aolin or
,imestone
Particulates of dolomite,
0aolin or lime stone
Particulates
Air Particulates 'ammonium
nitrate( and %:
2
Steam heated air :eat stress
3ater +apour
Particulates
%oise
.old dry air
Particulates
Polyethylene bags
.lay or diatomaceous
earth
Particulates 'ammonium
nitrates(
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,)
*+aporation
8eaction
%eutralization
Flash
*+aporation
Secondary
*+aporation
7iing
<ranulation
Prilling
-rying
Screening
.ooling
Storage
.oating @ bagging
Inspection Manual for Fertilizers Industry
e( "##oniu# Sulphate
Ammonium sulphate 'A.S( is a nitrogenous fertilizer with an
additional source of soluble sulphur which is a secondary plant
nutrient. /he ma)ority of its production is coming from co0ing of
coal as a byproduct. Ammonium sulphate is produced by the
direct reaction of concentrated sulphuric acid and gaseous
ammonia and proceeds according to the following steps.
+3 7eaction of "##onia and Sulphuric "cid1
,iquid ammonia is e+aporated in an e+aporator using 5B
bar steam and preheated using low pressure steam.
/he stiochiometric quantities of preheated gaseous
ammonia and concentrated sulphuric acid '=>.#$ wt4wt(
are introduced to the e+aporator K crystalliser 'operating
under +acuum(. /hese quantities are maintained by a
flow recorder controller and properly mied by a
circulating pump 'from upper part of the crystalliser to
the e+aporator(
23 &rystallization
/he reaction ta0es place in the crystallizer where the
generated heat of reaction causes e+aporation of water
ma0ing the solution supersaturated. /he supersaturated
solution settles down to the bottom of crystalliser where
it is pumped to +acuum metallic filter where the A. S
crystals are separated, while the mother liquor is recycled
to the crystalliser.
,3 :rying of the <et "##oniu# Sulphate &rystals
/he wet A.S crystals are con+eyed 'by belt con+eyors( to
the rotary dryer to be dried against hot air 'steam heated(
and then con+eyed to the storage area where it naturally
cooled and bagged.
Fig '5!( presents the process bloc0 diagram for ammonium
sulphate production.
f( "##oniu# hosphate
/here are two types of ammonium phosphate, namely: mono1
ammonium phosphate and di1ammonium phosphate. 7ono1
ammonium phosphate is made by reacting ammonia with
phosphoric acid, centrifuging and drying in a rotary dryer. -i1
ammonium phosphate requires a two1stage reactor system in
order to pre+ent loss of ammonia. A granulation process follows
with completion of the reaction in a rotary dryer which is heated
by a furnace using fuel.
/o produce mono1ammonium phosphate, ammonia to phosphoric
acid ratio is C.B in the pre1neutralizer and then 5.C in the
Environics July 2002
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Inspection Manual for Fertilizers Industry
granulator. For production of di1ammonium phosphate, the ratios
are 5.6 and 5.C in the pre1neutralizer and granulator respecti+ely.
/he resulting ammonium phosphate is then screened. /he
undersize particles are recycled bac0 to the granulation
operation, while the o+ersized particles are grinded first before
recycling to the granulator. After screening the fertilizer granules
are coated with specific material in order to regulate its
dissol+ing process in the soil when used.
Fig '52( illustrates the process bloc0 diagram for the
manufacturing of ammonium phosphate fertilizer.
Environics July 2002
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Inspection Manual for Fertilizers Industry
Fi) (*2 Process Flow Dia)ram +or .mmonium Sulphate
Manu+acturin)
Inputs Operations Outputs
,iquid ammonia
Steam
Ammonia emissions
:eat stress
'wor0 place(
Sulphuric acid
Ammonia @ acid mist
3astewater
'ammonium sulphate(
Air Steam :eated 3astewater
Solid waste 'crystals(
Polyethylene bags
Solid wastes
'bags and product
spills(
Environics July 2002
4+
*+aporation
8eactor @
.rystalizer
Filtration
-ehydration @
-rying
;elt .on+eyor
Sump
/an0
;agging
Inspection Manual for Fertilizers Industry
Fi) (*% Process Flow Dia)ram +or .mmonium Phosphate
Manu+acturin)
Inputs Operations Outputs
*+aporated Ammonia
Phosphoric acid
.ooling water
Fumes @ gases to
scrubber
Ammonia lea0s
Fuel for heater @ air
Ammonia
Furnace flue gases
Particulates of
ammonium phosphate
to cyclones
.ooling air Ammonia, particulates
Andersize recycled
Product size
Particulates @ %:
2
'wor0 place(
<rinded o+ersize recycled
Particulates
%oise
.oating materials Particulates to
collectors
Polyethylene bags
Ammonium Phosphate
Environics July 2002
42
8eaction
:ot <ranulation
@ -rying
Screening
<rinding
.oating
Storage
.ooling
;agging
Inspection Manual for Fertilizers Industry
g( &alciu# $itrate
.alcium nitrate is produced by dissol+ing the calcium carbonate
'lime stone( with nitric acid, according to the following reaction:
.a."
2
D !:%"
2
F .a'%"
2
(
!
D ."
!
D :
!
"
/he lime stone is transported to the site as small size stones and
lifted to the dissol+ing tower. /he nitric acid is fed to the bottom
of the dissol+ing tower and the formed calcium nitrate is fed to
the settling tan0. After settling, the ecess acid is neutralized
with ammonia. /he nitrogen content is ad)usted with ammonium
nitrate. /he fertilizer is produced in the liquid state and the
nitrogen content of the final product is ad)usted to the required
specifications using ammonium nitrate.
Fig '56( illustrates the process flow diagram for the production
of calcium nitrate fertilizers.
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Inspection Manual for Fertilizers Industry
Fi) (*/ Process Flow Dia)ram +or Calcium 6itrate
Inputs Operations Outputs
,imestone
%itric acid
."
!
@ acid mist
Solid wastes 'fla0es
of lime stone(
Solid waste .a."
2
Ammonia Fugiti+e ammonia
and acid mist
Ammonium nitrate
,iquid waste 'spills(
;arrels Spills of liquid
fertilizer
Environics July 2002
44
-issol+ing /ower
Settling
%eutralization
7iing '%
!
content
d)ustment(
Pac0aging
Stora)e o+ &i;uid
+ertili#ers
Inspection Manual for Fertilizers Industry
h( %rea
Area 'carbamide( is a high1concentration nitrogenous fertilizer,
with a 6B $ nitrogen content. It is produced from liquid
ammonia and gaseous carbon dioide at about 5EC1 5=CJ . and
52#1 56# bar, according to the following reactions:
."
!
D !%:
2
F %:
!
.""%:
6
'5(
%:
!
.""%:
6
O %:
!
."%:
!
D :
!
" '!(
/he second reaction is dehydration of the carbamate to produce
liquid phase urea.
/he urea plant consists of high and low pressure sections. /he
high pressure section is composed of:
Area synthesis including the high stripper and condenser.
Area rectifying operation.
3hereas, the low pressure section is composed of:
*+aporation.
8eco+ery.
Prilling.
.arbon dioide is supplied from the ammonia plant and
compressed in the centrifugal ."
!
compressor then introduced
into the bottom of the high pressure stripper, which is a part of
urea synthesis section. ,iquid ammonia is pumped from the
storage tan0 to the urea plant and is preheated to a temperature
around 5CJ .. /he high pressure %:
2
pump raises the pressure to
5B# bars and deli+ers it to the high pressure carbamate
condenser. %:
2
and ."
!
are fed to the synthesis section in the
molar ratio of ! for %:
2
4 ."
!
.
In the urea reactor most of the condensate carbamate is
con+erted to urea and water. /he reaction miture, lea+ing the
reactor from the o+erflow through internal down comer, is
distributed o+er the top of the stripper tubes. ."
!
gas is
introduced in counter flow. /he gases lea+ing the top of the
stripper are led into the high pressure carbamate condenser.
7a)or parts of the stripper off1gases are condensed gases and
non1condensed %:
2
, ."
!
. /hey are introduced into the bottom
of the reactor where the con+ersion of carbamate into urea ta0es
place. %on1con+erted %:
2
and ."
!
lea+e the reactor to the high
pressure scrubber, where ma)or parts of %:
2
and ."
!
are
reco+ered and mied with fresh %:
2
feed through the high
pressure e)ector.
/he urea carbamate solution lea+ing the bottom part of the
stripper is sprayed on a bed of ball rings in a rectifying column.
Environics July 2002
45
Inspection Manual for Fertilizers Industry
/he urea solution lea+ing the bottom part flows to a flash tan0
and then to the urea solution storage tan0 'about EC1 >C $
concentration(. /his solution is further concentrated to a melt '=>
$ urea( by e+aporation under +acuum in two stages. /he urea
melt is pumped to the prilling tower. /he prills are recei+ed on
con+eyors and transported to the bagging section.
/he condensate containing %:
2
, ."
!
and urea is pumped from
the %:
2
1 water tan0 to the upper part of the first desorber, which
is stripped by the o+erhead +apours of the second desorber. /he
bottom effluent of the first desorber is pumped to the hydrolyser
column. In the hydrolyser the urea is decomposed into %:
2
and
."
!
and fed to the first desorber after separation in the second
desorber. /he process condensate is discharged from the bottom
of the second desorber to the sewer system of the plant.
/he desired temperature of the prills ranges from BCJ . to B#J ..
If the temperature is >CJ .1 >#J . then the residual heat in the
prills causes some stretching and bursting for the polyethylene
bags after the bagging operation.
Fig '5#( shows the process flow diagram for the production of
urea.
Environics July 2002
46
Inspection Manual for Fertilizers Industry
Fi) (*0 Process Flow Dia)ram +or (rea Production
Inputs Operations Outputs
:eat stress
Area, ."
!
, %:
2
,iquid ammonia
.arbon dioide
Fugiti+e emissions
'%:
2
, ."
!
(
Fugiti+e emissions
'%:
2
, ."
!
, :
!
"(
Steam Fugiti+e emissions
'%:
2
, ."
!
, :
!
"(
.old air
Particulates, %:
2
,
."
!
, urea
8ecycled ."
!
, %:
2
Steam stripping agent 3astewater 'urea,
%:
2
, ."
!
(
Steam ,ea0s of %:
2
, ."
!
Particulates
%oise
Area formaldehyde
Polyethylene bags
Particulates
Environics July 2002
4'
8eactor
:igh Pressure
.ondenser
Stripping
8ectification
?acuum
*+aporation
Prilling
or granulation
.ondensate
.ollection
Flash /an0 E#$
First -esorption
Second -esorption
:ydrolyser
.oating @ ;agging
.ooling @ Screening
=>$
Inspection Manual for Fertilizers Industry
i( 8agging Section
/he produced fertilizers are sent to the bagging section by belt
con+eyors. Fertilizers are piled in this section and withdrawn by
rail scrapers which mo+es on a rail bars. ;y using for0s the
fertilizers slide down to the feed networ0 then to a sliding car
with small bun0er which ensure constant feeding. /he car slides
along the section to transport the product to an inclined belt
con+eyor or then to buc0et ele+ators and hammer mill. ;y a
screw con+eyor, the product is discharged to the final product
and pac0ed.
In the pac0aging stage a balance eist between the con+eyor and
the pac0aging bun0er at which a le+el meter is fied. /he
bun0ers feed the balance which consequently feed pac0aging
operation in which polyethylene bags are filled and transported
by belt con+eyors to the truc0s.
Environics July 2002
4)
Inspection Manual for Fertilizers Industry
Ser'ice (nits and Related Pollution Sources
7edium and large size plants will ha+e some4all of the following ser+ice
and auiliary units. /hese units can be pollution sources and therefore
should be inspected and monitored. Fig '5B( shows the +arious units
with their corresponding raw materials and potential pollution sources.
2.%.* ,oilers
;oilers are used to produce steam for:
heat supply to the processes, reaction 'steam reforming( and ." shift
con+erter 'in ammonia production and other processes utilizing steam(.
electric power generation.
.on+entional steam1producing thermal power plants generate electricity
through a series of energy con+ersion stages. Fuel is burned in boilers
to con+ert water to high1pressure steam, which is then used to dri+e the
turbine to generate electricity.
/he gaseous emissions generated by boilers are typical of those from
combustion processes. /he ehaust gases from burning fuel oil '7azot(
or diesel oil 'solar( contain primarily particulates 'including hea+y
metals if they are present in significant concentrations in the fuel(, sulfur
and nitrogen oides 'S" and %"( and +olatile organic compounds
'?".s(.
/he concentration of these pollutants in the ehaust gases is a function
of firing configuration 'nozzle design, chimney height(, operating
practices and fuel composition.
<as1fired boilers generally produce negligible quantities of particulates
and pollutants.
3astewater is generated as blowdown purged from boilers to 0eep the
concentration of dissol+ed salts at a le+el that pre+ents salt precipitation
and consequently scale formation. /he blowdown will be high in /-S.
In the case of power plants, water is used for cooling the turbines and is
also generated as steam condensate. /he amount of wastewater
generated depends on whether cooling is performed in open or closed
cycle and on the recycling of steam condensate. .ontamination may
arise from lubricating and fuel oil.
2.%.2 Water !reatment (nits
/here are different types of water used in industry. -epending on the
application and the water source, different treatment processes are
applied.
a3 .ater Softening for #ediu# hardness <ater
.alcium and magnesium ions are remo+ed from hard water by cation
echange for sodium ions. 3hen the echange resin has remo+ed the
ions to the limits of its capacity, it is regenerated to the sodium form
with a salt solution 'sodium chloride( in the p: range of B1>. /his is
performed by ta0ing the softener out of ser+ice, bac0washing with the
salt solution, rinsing to eliminate ecess salt, then returning it to ser+ice.
/he treated water has a hardness le+el of less than 5 ppm epressed as
calcium carbonate.
Environics July 2002
4*
Inspection Manual for Fertilizers Industry
-3 .ater softening for very high -icar-onate hardness
3ater from wells and canals is pre1treated before softening. 3ater is
treated first by the lime process, then by cation echange. /he lime
process reduces dissol+ed solids by precipitating calcium carbonate and
magnesium hydroide from the water. It can reduce calcium hardness to
2# ppm if proper opportunity is gi+en for precipitation. A coagulant such
as aluminum sulfate 'alum( or ferric sulfate is added to aid magnesium
hydroide precipitation. .alcium hypochlorite is added in some cases.
.urrently the use of organic poly1electrolytes is replacing many of the
traditional inorganic coagulant aid. Sludge precipitates and is discharged
to disposal sites whereas the o+erflowing water is fed to a sand filer
followed by an acti+ated carbon filter that remo+es any substances
causing odor and taste. A micro filter can then be used to remo+e
remaining traces. A successful method to accelerate precipitation is
contacting pre+iously precipitated sludge with the raw water and
chemicals. /he sludge particles act as seeds for further precipitation.
/he result is a more rapid and more complete reaction with larger and
more easily settled particles.
c3 .ater :e#ineralization
3ater demineralization units are indispensable units in industrial plants.
/hese units pro+ide the rele+ant water, after remo+ing the soluble salts,
for pressure boilers and dematerialized necessary for process 'as process
water for nitric acid, sulphuric acid .. etc(. /he remo+al of salts in the
raw water is carried out by special resins through ion echange. /he raw
water is pumped to cation, anion 'and mied bed( echangers. /he
resins when ehausted 'saturated with salts( are regenerated using
+arious chemicals such as sodium chloride, hydrochloric acid or
sulphuric acids and sodium hydroide. /he effluents during these
regeneration processes 'twice a day( represent a considerable source of
pollution.
2.%.% Coolin) !owers
.ooling water is used etensi+ely in industry. -uring the cooling
process, water heats up and can only be reused if cooled. .ooling
towers pro+ide the means for recycling water and thus minimizing its
consumption. /he cooling effect is performed through partial
e+aporation. /his causes an increase in the concentration of dissol+ed
salts which is controlled by purifying some water 'blowdown(. /he
blowdown will be high in /-S.
2.%./ Compressors
Se+eral types of compressors are needed in the fertilizers plants,
including the ammonia, steam, gas and air compressors. .ompressors
consume a considerable quantities of lube oils for lubrication and
cooling purposes, in addition to electricity. /he ma)or resulting
pollutants are noise affecting wor0ers and the spent oils.
Environics July 2002
50
Inspection Manual for Fertilizers Industry
,ube oils are essential for se+eral parts of the compressors. It utilizes as
a pillow which facilitate the re+ol+ing motion, in addition to the
absorption of resulted heat due to friction. 3hen the compressor is
started1up a pump drafts the oil from its storage tan0, to a filter and an
oil cooler. /he lube oil, after passes through different parts of the
compressor, is collected bac0 in the oil tan0.
Ammonia compressing is composed of two stages, the first includes two
cylinders and the second four. %o greasing is applied inside the
cylinders, but only the other parts are being greased in order to lower the
friction. /he temperature of a gas arises by compression, hence it needs
to be cooled before any further compression. .ompressing is done by
the piston inside the cylinder, in which the gases in front of the piston
are being pressed until their pressure equalize the repelling pipe
pressure. /his opens the discharging +al+e and compressed gases eit
into their path. /he suction +al+e is consequently opened and gases
introduce the cylinder behind the piston. /hese types are named the
frequency compressors. <aseous lea0s may result from the compressors,
which generate a pollution problem in the wor0 place of the unit. A good
chec0 should be implemented for the equipment in order to a+oid
operating problems, such as clogging in the filter of oil suction pump,
lea0s from the non1return +al+e, bro0en pipelines of any other parts,
temperature increasing than usual, decreasing in cooling efficiency N
etc. /he compressorP motor is cooled by cold air.
2.%.0 &a"oratories
/here are se+eral laboratories in the fertilizers plants which are
responsible for different acti+ities, as follows:
8esearch laboratory, responsible for de+eloping, through research and
analysis, new types of fertilizers as well as studying the different effects
on soil and plant.
Muality control laboratory, responsible for the analysis of the different
products and comparing the findings with the standard specifications. It
also analyze the raw materials inputs to the different units of the plant.
*n+ironmental laboratory, responsible for the collection of periodical
routine and sudden random samples to control air and water pollution. It
is also responsible for the performance of water and wastewater
treatment units, through periodic analysis for the inlet and outlet
streams.
-ifferent types and quantities of hazardous chemicals are used for
different testing and analysis. Proper handling and storage are required
for compliance with en+ironmental law.
2.%.5 Wor<shops and 1ara)e
,arge facilities ha+e electrical and mechanical wor0shops for
maintenance and repair purposes. *n+ironmental +iolations could be
due to:
%oise
Environics July 2002
5+
Inspection Manual for Fertilizers Industry
8inse water contaminated with lube oil
Pollution in the garage area will depend upon the ser+ices offered. /he
presence of a gasoline or diesel station implies fuel storage in
underground or o+er the ground tan0s that require lea0 and spill control
plans.
8eplacing lube oil implies discharge of spent oil to the sewer lines or selling it
to recycling stations. 3ashing agents and sol+ents may be used.
2.%.7 Stora)e Facilities
/he specifications for the storage facilities depend on the stored
material. Fuel is used for the boilers, cars and deli+ery truc0s. It is
stored in underground or o+er ground lined tan0s. Asually, fuel oil
'7azot(, gas oil 'solar( or natural gas are used as fuel. Acids such as
sulphuric or nitric or phosphoric acids are stored in large capacities
tan0s.
2.%.8 Wastewater !reatment Plants
Although a 33/P is a pollution abatement measure, it has to be
inspected and monitored for potential pollution. Pollution may be due
to malfunctioning or improper management. -isregarding treatment of
boilers and cooling towers blowdown, which is by far the largest
wastewater problem in the industry, se+eral treatment schemes ha+e
been used. 7ost approaches ha+e been based on the origin of the
product, that is phosphate or nitrogenous fertilizer.
/he effluent streams can be characterized as either a phosphoric acid
effluent or an ammonia effluent. /he phosphoric acid effluent is high in
fluoride concentration, low in p:, high in phosphate and in suspended
solids. Standard practice has been to contain the water for reuse,
allowing enough time for solids sedimentation. /he problem is that fresh
water addition may result in o+erflow of the retained water. /he
retention ponds should be carefully designed. If o+erflow is e+ident, it
must be treated with lime and clarified.
A slightly more sophisticated method for discharging o+erflow water is
with a two1stage liming process. /he first lime treatment brings the p:
up to 2 or 6 and reduces the fluoride concentration to !C1 !# mg4 l and
the P concentration to #C1 BC mg4 l. /he .aF! precipitate is settled out
and the effluent is treated again with lime to raise the p: to B or E. /he
F and P concentrations are reduced to about 5C mg4 l. the water is
clarified and released to a recei+ing stream. /he two1stage fluoride
remo+al process of lime precipitation followed by alum1polyelectrolytes
flocculation and sedimentation was found to be wor0able. 7aimum
precipitation of fluoride with lime occurs at a p: greater than or equal to
5! and optimum coagulation with the alum1polyelectrolyte occurred at a
p: of about B to E.
/he other effluent type is characteristic of ammonia production and
ammonia containing products. 7ost of the contamination comes from
the production of the ammonia itself. It is characteristically high in
ammonia from effluent gas scrubbing operation and high in ammonia,
Environics July 2002
52
Inspection Manual for Fertilizers Industry
total suspended solids and carbamate. /hese effluents require a p:
ad)ustment and settling.
/he treated effluent is discharged to the recei+ing media and a final
sludge is remained. Safe sludge disposal should be implemented, due its
high content of hazardous constituents such as hea+y metals,
phosphorous, ammonia and silicates.
2.%.9 Restaurants, Washrooms and 4ousin) Comple=
/hese facilities will generate domestic wastewater as well as domestic
solid waste.
Environics July 2002
5,
Inspection Manual for Fertilizers Industry
Fi) (*5 Ser'ice (nits and their Related Pollution Sources
Inputs Ser'ice (nits Pollution
3ater
,ime D chemicals
Fuel
Sludge
;ac04wash
;lowdown '/-S(
Flue <ases
:ot 3ater
.ooling /ower
;lowdown '/-S(
.hemicals
3astewater
:azardous 7aterials
'handling(
,ube "il
Floor and equipment rinse
water
.leaning .hemicals
"ily 8inse 3ater
3aste oils
Solid 3astes
,ube oil
.ooling water
Spent oil
Fuel
"il
8inse 3ater
"ily rinse water
Solid wastes
3aste oils
Fuel
.hemicals
Spills
:azardous material
3astewater /reated water
Sludge
3ater
Solid wastes
Sanitary 3astewater
Environics July 2002
54
.ooling
/owers
8estaurant
and
restrooms
3astewater
/reatment
Anits
Storage
<arage
,aboratory
*lectrical
@
7echanical
3or0shops
Softeni
ng
Anits
;oilers
Stea
m
/reatm
ent
.ompressor
s
Inspection Manual for Fertilizers Industry
>missions, >++luents and Solid Wastes
Fertilizers industry manufacturing processes originate is gas,
contaminated liquid effluents in addition to dust and solid by1products.
/hese wastes pollute air, water as well as impair soil. Pollution
problems arise from low processes efficiency and4or inefficient dust
collecting systems, gas scrubbing 'if it does eist( and most important is
the lac0 of a pro+en recycle of such reco+ered contaminants to the
process streams.
.ir >missions
/he ma)or emission in phosphoric and nitrogenous fertilizers cited here
below includes particulates, sulphur oides, hydrogen fluoride 'and
compounds .a F
!
SiF
6
( phosphogypsum, phosphoric acid, ammonia,
%"
Source (2
p: !
.
C
E
5
.
C
5
."- m
g
4
l
!
!
.
2
>
B
.
6
;"- m
g
4
l
5
5
.
2
#
E
/otal nitrogen mg4 l 5 B
.
#
Settleable solids mg4 l 1 C
.
6
/otal residue at 5C#
o
. mg4 l >
E
2
2
6
!
=
5
/otal +olatile residue at ##C
o
.
mg4 l !
6
B
5
C
E
B
B
/otal suspended solids mg4 l 5
#
>
5
B
/otal dissol+ed solids mg4 l >
#
>
2
2
6
E
#
Environics July 2002
66
Inspection Manual for Fertilizers Industry
/otal phosphate mg4 l B
.
>
=
6
C
Sulphate mg4 l #
!
!
#
C
C
/otal hardness mg4 l B
#
1
.alcium hardness mg4 l 2
!
.
#
1
Fluoride mg4 l 5
6
C
C
5
#
!
C
C
Soluble silicate mg4 l !
5
C
5
>
C
Iron mg4 l 5
.
5
5
5
#
Source '5(: cooling water.
Source '!(: process water 'washing water(.
-3 $itrogenous Fertilizers
3astewater is considered the ma)or pollution problem in
such plants. A number of process wastewater streams
from the nitrogenous fertilizer industry ha+e been
identified. 3astewater is analyzed in terms of ammonia,
nitrates, organic nitrogen and hydrogen ions
concentration 'p:(.
"##onia roduction
In ammonia production, wastewater is generated
from process condensate stripping. .ooling the
synthesis gas after low temperature shift
con+ersion forms a condensate containing %:2,
."!, methanol '.:2":(, and trace metals.
.ondensate steam strippers are used to remo+e
%:2 and methanol from the water. Stripped
condensate can be reused as boiler feed water
after treatment of ion echange. In some cases,
the process condensate is used for feed gas
saturation and thus recycled.
Environics July 2002
6'
Inspection Manual for Fertilizers Industry
3astewater is contaminated with traces of
ammonia and oils from compressing gas unit.
*missions to water may also occur due to the
scrubbing of waste gases containing ammonia if
gases are not reco+ered in a closed loop so that no
aqueous ammonia emissions occur.
$itric "cid roduction
%itric acid production generates relati+ely little
wastewater since there is no process wastewater
source. Steam condensate generated in
nitrogenous fertilizer processing is characterized
by dissol+ed and suspended solids, al0alinity, and
hardness. /he ammonia +aporizer blow1down
should ha+e the ammonia +aporized and
reco+ered into the process. /he waste oil should
be reprocessed.
"##oniu# $itrate roduction
3astewater effluent is discharged from cooling
tower blowdown, bac0wash from multi1media
filters and from equipment and floor washing.
,oss of ammonium nitrate to drain from a large
number of sources is a potential problem for all
ammonium nitrate plants. .auses are different
0inds of lea0s and washings.
Ammonium nitrate manufacturing produces
process wastewater in the neutralization process,
the e+aporation unit, and air cooling equipment.
/he +acuum condenser in ammonium nitrate
plants is a source of wastewater. 7ost scrubbing
operations are also a source of wastewater. /he
steam condensate lea+ing the neutralizer can be
purified. Purification can be achie+ed by
stripping, distillation and membrane separation
processes as re+erse osmosis. Ion echange can
also be considered but ther are some safety
concerns which must be addressed. /he steam can
be used in the e+aporator or to preheat and
e+aporate ammonia and to preheat nitric acid. /he
solution from wet scrubbers is normally recycled.
%rea roduction
Steam is used in considerable amounts in this
production line, therefore, steam condensate is the
ma)or effluent. Fugiti+e ammonia, carbamate and
particulates are dissol+ed in the steam condensate
forming a pollution source for this effluent if not
recycled.
Environics July 2002
6)
Inspection Manual for Fertilizers Industry
"##oniu# Sulphate roduction
3astewater includes the blowdown from boilers,
water from the wet scrubbers and floor drains is
redirected to the process for recapture of
ammonium sulphate. 3astewater contains traces
of ammonia, sulphate and acidity.
Floor drains collect liquid spills and bleed line
discharges from circulating pumps and directs the
liquids to the sump tan0 from which it is pumped
bac0 to the crystalizer. /he sump tan0 also
collects the bottom drain line discharges from the
crystalizer. "+erflow, if eist, from the sump tan0
could generate another source of pollution. Steam
condensate is another source of pollution to the
wastewater.
:i5"##oniu# hosphate roduction
Spills of acids 'sulphuric and phosphoric acids( and
ammonia lea0s are dissol+ed in floor washing wastewater
and polluting the effluent stream from this unit. Also
contaminated wastewater from scrubbers is generated.
&alciu# $itrate
%itric acid is used in this unit, hence spills of this acid
highly pollute the effluent stream. 7oreo+er, spills of
liquid fertilizer and particulates from the solid fertilizer
and fugiti+e ammonia are dissol+ed in the floor washing
water generating another pollution source.
Methanol roduction
3astewater contaminated with alcohol produced from
distillation of the product is considered the ma)or
polluting source in this unit.
Solid Wastes
For all fertilizers plants, solid materials may be found in storage piles, settled
dust and other similar forms. /he following are the ma)or solid wastes in
different production lines of fertilizers.
a3 hosphate Fertilizers
Single Superphosphate roduction
"ff1specification product, products spills, and dusts
collected in emission control systems are potential
sources of residual wastes. Products are occasionally
suspended or canceled, lea+ing stoc0piles of residual
product.
Environics July 2002
6*
Inspection Manual for Fertilizers Industry
!riple Superphosphate roduction
Sources of solid wastes in this production line are spent
containers, wastewater treatment sludges, and spent
filters. 7any of these wastes are transported offsite for
disposal. :owe+er, with good house0eeping techniques
and dedicated systems, some of these wastes may be
recycled bac0 into the process instead of being wasted.
hosphoric "cid roduction
"ne of the largest solid wastes in this production unit is
phosphogypsum. Approimately 5.# tons of
phosphogypsum is produced per ton of phosphate roc0
fed, or # tons per ton of phosphoric acid produced
'epressed as P
!
"
#
(. <ypsum 'calcium sulphate
dihydrate( is a mineral which also occurs in nature.
Phosphogypsum is produced by the reaction of phosphate
roc0 with sulphuric acid during the process of producing
phosphoric acid.
/he use of waste phosphogypsum for other purposes has
been widely encouraged, but economic and4or quality
problems and4or the demand for the resulting products
frequently inhibit or pre+ent this. /hese problems relate
not only to the impurities in the gypsum, but also to its
relati+ely high moisture content. Plasterboard, plaster,
and cement are the main possibilities. It is also possible
to recycle phosphogypsum in sulphuric acid production.
-umping gypsum on land is not possible e+erywhere
because the material settles and dries slowly and requires
an adequate land area and certain climatic and soil
conditions where the stac0 is situated. <ypsum stac0s are
being increasingly regulated in terms of lining and cap
systems to pre+ent contaminated leaching or runoff .
.admium is a hea+y metal which accumulates in li+ing
systems and can become toic abo+e certain limits. /he
quantity of cadmium contained in a phosphatic fertilizer
depends on the source of the roc0 or waste material from
which it was made. /he cadmium content of phosphate
roc0s +aries from almost zero to o+er 2CC mg40g P!"#.
/he acidulation of phosphate roc0 partitions the cadmium
between the fertilizer product and the by1products,
mainly the phosphogypsum arising from phosphoric acid
production.
Sulphuric "cid roduction
Spent catalyst is generated from this production line and
usually returned to the licensor. /he +anadium content of
the ?
!
"
!
catalysts can be reclaimed for further use. /his
ser+ice is usually pro+ided by the catalyst manufacturer.
Environics July 2002
'0
Inspection Manual for Fertilizers Industry
/he metal can be recycled as +anadium salts or
ferro+anadium for steel production.
-3 $itrogenous Fertilizers
"##onia roduction
Solid wastes are generated due to the usage of many
catalysts types and quantities. /he spent catalysts can not
be purified or recycled, hence, they create a disposal
problem which should be chec0ed. /hese catalysts are
considered hazardous, due to their hea+y metals content
'chromium and nic0el(. Another solid waste problem is
the filling material for absorption tower. /hey are
consumed and disposed off1site.
.atalysts used in the steam reforming process need to be
replaced e+ery two to si years. Spent catalysts contain
oides of hea+alent chromium, zinc, iron, and nic0el.
/hey are typically returned to the manufacturer or other
metal reco+ery companies for recycling and reclamation
of +aluable materials.
$itric "cid roduction
Spent catalyst from the reactor and filter ca0e and cloth
generated from the filter are considered the ma)or solid
wastes generated from this unit. Asually spent catalyst is
sent to the suppliers and it must not be disposed in
dumping sites due to its hazardous nature.
"##oniu# $itrate roduction
-olomite and clay from the miing and coating
operations are the ma)or solid wastes from this unit as
well dump product.
"##oniu# Sulphate roduction
Ammonium sulphate crystals during con+eying and
bagging are collected and recycled.
"##oniu# hosphate roduction
Spills of the fertilizers in the bagging section are
collected and recycled.
%rea roduction
Prills coating material in the bagging section are collected
and recycled.
Wor< >n'ironment
Se+eral pollutants are generated in the wor0 en+ironment within the
fertilizers plants, these include the following:
Environics July 2002
'+
Inspection Manual for Fertilizers Industry
Fugiti+e gases and +apours inside the production units, which
+ary according to the production line. In phosphatic fertilizers
plants, these emissions include fluoride compounds ':F, SiF
6
and :
!
SiF
B
( and %"