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THERMODYNAMIC ESTIMATION

OF THE ENVIRONMENTAL IMPACT


OF MINERAL FERTILIZERS
PRODUCTION
Zornitza Kirova - Yordanova
e-mail zkirova@btu.bg
University Prof. Assen Zlatarov
Department of Inorganic Technology
8010 Bourgas, Bulgaria

Mineral fertilizers and


global food provision

urea

It is estimated that about 40% of the world's protein needs


are derived from atmospheric nitrogen fixed by the Haber
-Bosch process and its successors to produce ammonia.
October 2002
International Fertilizer Industry Association (IFA)
1996-2004

IFA Statistics 2004

Mineral fertilizers and environment:


Production
Distribution
Application

Mineral fertilizers production and environment:


Natural resources consumption
Emissions and wastes

Natural resources consumption


Natural gas for production of ammonia and all
nitrogen containing fertilizers
Phosphate rock for production of phosphoric acid
and all phosphorous containing fertilizers
Potassium minerals for potassium fertilizers
production

Emissions and wastes from ammonia production


Basic reaction
Natural gas + Water (Steam) + Air
3 H2 + N2 + CO2 Ammonia + CO2
Emissions into atmosphere :
Vent gas from CO2 removal unit: 98,5 99% CO2
Flue gas from reforming furnace: 8-12% CO2; <300 ppm NOx

Liquid effluents:
Process condensate (from surplus steam): 0,1% NH3, 0,1% CH3OH

Emissions and wastes from urea production


Basic reaction
2NH3 + CO2 NH2CONH2 + H2O
Emissions into atmosphere :
Vent gases: NH3
Air from prilling towers: NH3 , urea dust

Liquid effluents:
Process condensate (water,formed by the reaction): NH3, urea

Wastefluegas
fgfffFlfow
NH3liquid
CO2
Ammonia
Steam
Plant

Ar

Air
Natural
Gas

Electricity

Water

BFW

Steam
Thermal
and
Steam&
Power
PowerPlant
Plant

Urea
Urea
Plant

WasteProcess
Condensate
NH3 WasteProcess

Condensate
Treatment

Steam
Electricity
NH4COONH2
SteamCondensate
PurifiedProcessCondensate

Air

Electricity
Steam

Wastefluegas

Figure 1. Block flow diagram of an urea production plant

Emissions and wastes from nitric acid production


Basic reactions:
4NH3 + 5O2 (Air) 4NO + 6H2O
2NO + O2 2NO2
3NO2 + H2O 2HNO3 + NO

Undesirable parallel reactions of ammonia oxidation:

4NH3 + 4O2 (Air) 2N2O + 6H2O


4NH3 + 3O2 (Air) 4N2 + 6H2O
Emissions into atmosphere :

Tail (waste) gas: NOx , N2O

Liquid effluents: none

Emissions and wastes from ammonium nitrate


production
Basic reaction
NH3 + HNO3 (45-62%) NH4NO3
Emissions into atmosphere :
Process steam: NH3, ammonium nitrate fine dust and droplets
Air from prilling towers: NH3 , ammonium nitrate dust

Liquid effluents:
Process condensate (water from nitric acid solution): NH3, NH4NO3

CO2

Wastefluegas

NH3

Ar

Air

NaturalGas

Steam

Ammonia
Plant

Electricity

Water
Air

HNO3
NitricAcid Steam

NH3

Plant

Process
Condensate

BFW

Thermal
Thermal
steam
Steamand
and
Power
power
Plant
plant

Ammonium
Nitrate
Plant

Electricity
Tail
Gas
Steam
Electricity
Condensate
Steam
SteamCondensate
Electricity

Ammonium
Nitrate
Process
Condensate
NH3

NH4NO3

Waste
Process
Condensate
Treatment

PurifiedCondensate

Steam

Wastefluegas

Figure 2. Block flow diagram of an ammonium nitrate production plant

Emissions and wastes from wet process


phosphoric acid production
Basic reaction

3Ca3(PO4)2.CaF2 + 10 H2SO4 + 20 H2O

6 H3PO4 + 10 CaSO4.2H2O +2 HF

Emissions into atmosphere :


Air from handling and grinding of phosphate rock: dust
Air from reactors: HF, SiF4

Liquid effluents:
Filtration waters: Phosphates and fluorides

Solid wastes:
Phosphogypsum CaSO4.2H2O

As the pollutants, released into the environment


from the fertilizers plants, are usually products,
semi-products or feedstocks of the production
processes, the recycling and recovery of the
emissions leads to decreasing both the
feedstocks and energy consumption.

Since 1960s, the production of mineral fertilizers


have made enormous progress in reducing natural
resources consumption as well as emissions

Exergy and environment:


Natural resources consumption
Emissions and wastes
Natural resources consumption :

Cumulative Exergy concept (Szargut et al.):


Cumulative Exergy Consumption (CExC)
Cumulative Degree of Perfection (CDP)
Emissions and wastes

Exergy as a measure of the environmental


impact of the emissions and wastes ?

Why exergy ?

+ The exergy of a system


is the potential of the
system with respect to the
environment

-The thermodynamic environment is not equal


to the real environment
-The exergy is not a specific indicator

How to use exergy


as environmental indicator ?
Exergies of the pollutants and waste flows
Exergies of the natural resources, accumulated in the
waste flows
Exergy of the additional emissions, arising as a result of
the waste flows treatment process
Total exergy of the emissions from the process and from
the waste flows treatment
Total net reduction of the emissions exergy as a result of
the waste flows treatment with recycling of the pollutants
back into the process
Exergy and cumulative exergy consumption of natural
resources in some processes of the waste flows treatment

Exergies of the emissions and waste flows


Exergy of the pollutants only ?
or
Exergy of the whole discharged flow ?

Exergies of the emissions and waste flows


Whole exergy ?
or
a some part of exergy ?
Thermal exergy
Mechanical exergy
Chemical exergy

Chemical exergy as a rough measure of the


environmental impact of the pollutants and
emissions ?
The potential of the emissions
to damage the environment,
depends on their chemical
composition and especially,
on the concentrations and
properties of the pollutants.
The temperature and the
pressure of the fluids and solids,
discharged from chemical plants,
are close to the environmental
parameters, therefore, their
physical exergy is rather small.

Some examples
Chemical exergy of gaseous, liquid and solid flows,
released to the environment from nitrogen and
phosphorous fertilizers production plants
Chemical exergy of the individual pollutants in the
same flows

The chemical exergies of the pollutants (GJ/t pollutant)


are usually very high, which is in agreement with their
harmfullness, at least qualitatively
Ammonia
Urea
Ammonium nitrate
NOx (as NO2)
N2O
CH3OH
Soluble phosphates (as H3PO4)
Fluor as HF
CO2
CaSO42H2O
Insoluble phosphates (as Ca10(PO4)9F2)
Fluor as CaSiF6

20.024
11.372
3.73
1.2192
2.4104
22.649
2.648
3.8544
0.4576
0.1501
0.0203
1.407

The chemical exergies of the same pollutants,


referred to 1 tonne of the product, are small,
because of the low contents of the pollutions in
the released flows.
The exergies of the emitted flows as a whole,
(referred to 1 tonne of the flow) are rather high,
especially in the case of the liquid effluents,
higher than the exergies of all the pollutants in
them. The reason is that the exergy of the pure
liquid water is rather high at the specified
environmental parameters.

Emissions to atmosphere and liquid effluents


from urea production
Chemical exergy of Chemical exergy of
the pollutants
the emitted flows

Gaseous emissions
and liquid effluents

Pollutant

Air from prilling towers in


urea production (46.5% N)

NH3
urea
dust

mg/Nm3
8-13
12-110

Vents from NH3 absorbers

NH3

14 g/Nm3

Waste process waters


before treating
Waste process waters
after treating in new
plants [6,7]

Concentration

GJ/t GJ/t
pollutant product

GJ/t
flow

GJ/t
product

20.024 0.0087
11.372 0.0315

0.00078

0.0402

20.024

0.037

0.0003

0.044

NH3
urea

mg/l
110-340
200-770

20.024
11.372

0.006
-0.018
0.006
-0.024

0.166
-0.167

0.447
0.477

NH3
urea

5 mg/l
1 mg/l

20.024
11.372

0.00005
5.6.10-6

0.1614

0.0807

0,02
0,018

NH3 to air from


prilling towers

0,016

Urea dust to air


from prilling
towers

0,014
0,012
GJ/t urea

0,01

NH3 to air from


vents

0,008
0,006
0,004

NH3 in waste
water

0,002
0
Existing
Existing
New plants
plants
plants lower
upper limit
limit

Urea in waste
water

Fig. 3. Chemical exergy of the emissions to air and to water


from urea production plants

0,12
0,11
0,1
0,09
0,08
0,07
GJ/t urea 0,06
0,05
0,04
0,03
0,02
0,01
0

Waste water

Emissions to air
from prilling
towers
Emisiions to air
from vents

Existing plants
upper limit

Existing plants
lower limit

New plants

Fig. 4. Chemical exergy of the emissions to air and to water


from urea production plants

0,24
0,22
0,2
0,18
0,16
0,14
GJ/t urea 0,12
0,1
0,08
0,06
0,04
0,02
0

Urea dust to air


from prilling
towers
NH3 to air from
prilling towers
Inerts to air
from vents
NH3 to air from
vents
Urea in waste
water
NH3 in waste
water
Existing plants Existing plants
upper limit
lower limit

New plants

H2O in waste
water

Fig. 5. Chemical exergy of the emissions to air and to water


from urea production plants

H2O

0,7

NH3

0,6

CH3OH

0,5

N2+O2+H2O

GJ/t NH3 0,4

CO

0,3

NOx

0,2

CO2

0,1

H2+N2

0
Vent gases from
CO2 removal

Flue-gas from
the reforming
furnace

Process
condensate

CO2

Fig. 6. Chemical exergy of the emissions to air and liquid effluents


from ammonia production plants

Emissions to atmosphere from nitric acid production


Gaseous
emissions

Pollutant

Tail gas
before
treatment

NO
NO2
N2O

NOx
Tail gas after (as NO2)
N2O
treatment

Chemical exergy of the Chemical exergy of the


pollutants
emitted flows
Concentration
ppmv
GJ/t GJ/t
GJ/t
GJ/t
pollutant product
flow
product
NO+NO2
800-2500
700-1300

2,966 NO+NO2
1.219 0.01-0.03
2.4104 0.01-0.02

50-200
50-1300

1.219
2.4104

0.0007-0.0022
0,001-0,02

0.029-0.040

0.120-0.167

0.028-0.138 0.116-0.542

Tail gas treatment processes:


Extended absorption of NOx with water
Selective catalytic reduction (SCR) of NOx with ammonia
Non-selective catalytis reduction (NSCR) of NOx and N2O with natural gas

Fig. 7. Flowsheet of a medium pressure/high pressure nitric acid


production plant with non-selective catalytic reduction (NSCR)
of NOx and N2O with natural gas

Emissions to atmosphere (tail gas) from nitric


acid production
Exergies of the pollutants and of the tail gas
Exergy of the additional emissions, arising as
a result of the tail gas treatment processes
Total exergy of the emissions from the process
and from the tail gas treatment
Exergies of the natural resources, accumulated
in the tail gas

0,09

NOx in tail gas before


treating

0,08
0,07

NOx in tail gas after


treating

0,06

N2O in tail gas before


treating

GJ/t HNO3 0,05


(100% ) 0,04
0,03

N2O in tail gas after


treating

0,02

NH3 in tail gas after SCR

0,01

CO in tail gas after NSCR

0
Extended
absorption

SCR

NSCR

Fig. 8. Chemical exergy of the gaseous polutants from dual pressure


nitric acid production plants before and after the tail gas treating:
1 Medium pressure/High pressure plant with extended absorption;
2 Low pressure/Medium pressure plant with SCR;
3 Medium pressure/High pressure plant with NSCR

0,6
0,5
0,4

Before treating
GJ/t HNO3
(100% )

After treating

0,3
0,2
0,1
0

Extended
absorption

SCR

NSCR

Fig. 9. Total chemical exergy of the gaseous emissions


from dual pressure nitric acid production plants
before and after the tail gas treating:
1 Medium pressure/High pressure plant with extended absorption;
2 Low pressure/Medium pressure plant with SCR;
3 Medium pressure/High pressure plant with NSCR

0,25
NOx in tail gas
before treating
0,2

GJ/t HNO3
(100% )

NOx in tail gas after


treating
N2O in tail gas after
treating

0,15

N2O in tail gas after


treating
0,1

NH3 in tail gas after


SCR
CO in tail gas after
NSCR

0,05

0
Extended
absorption

SCR

NSCR

Fig. 10. Cumulative exergy of the gaseous polutants from dual pressure
nitric acid production plants before and after the tail gas treating:
1 Medium pressure/High pressure plant with extended absorption;
2 Low pressure/Medium pressure plant with SCR;
3 Medium pressure/High pressure plant with NSCR

2,2
2
1,8
1,6
1,4

GJ/t HNO3
(100% )

Exergy
consumption

1,2
1
0,8

Cumulative
exergy
consumption

0,6
0,4
0,2
0
-0,2

Extended
absorption

SCR

NSCR

Fig. 11. Exergy consumption and cumulative exergy consumption for NOx
abatement in dual pressure nitric acid production plants:
1 Medium pressure/High pressure plant with extended absorption;
2 Low pressure/Medium pressure plant with SCR;
3 Medium pressure/High pressure plant with NSCR

Some results of exergy balances of nitric acid production


plants with different tail gas treatment processes
Low pressure/
Medium
pressure plant
with SCR

Medium
pressure/High
pressure plant
with extended
absorption

Medium
pressure/High
pressure plant
with NSCR

Exergy losses total

4.970

6.644

5.049

incl. exergy losses in the tail


gas treatment and energy
recovery systems

0.441

2.151

0.594

Degree of Perfection, %

17.50

28.30

30.81

Degree of Perfection of the


tail gas treatment and energy
recovery systems,%

65.06

45.34

47.53

13.896

7.478

9.822

7.20

13.37

10.18

EXERGY INDICES

CExC for nitric acid & power


or steam production, GJ/GJ
CDP for nitric acid & power or
steam production, %

0,008

NH3 in waste water

0,007
0,006

NH4NO3 in waste
water

0,005

GJ/t
ammonium 0,004
nitrate

NH3 to air from prilling


towers

0,003

NH4NO3 dust to air


from prilling towers

0,002
0,001

NOx and HF to air from


vents

Ammonium nitrate

Stabilized
ammonium nitrate

Fig. 12. Chemical exergy of the emissions to air and to water from
ammonium nitrate production plants:
Fertilizer grade ammonium nitrate (34,5% N) and
Stabilized ammonium nitrate (31.6% N, 2,7 % P2O5)

0,01
0,009
0,008

Waste water

0,007
0,006
GJ/t
ammonium 0,005
nitrate
0,004

Vents
Air from
prilling towers

0,003
0,002
0,001
0

Ammonium nitrate

Stabilized
ammonium nitrate

Fig. 13. Chemical exergy of the emissions to air and to water from
ammonium nitrate production plants:
Fertilizer grade ammonium nitrate (34,5% N) and
Stabilized ammonium nitrate (31.6% N, 2,7 % P2O5)

0,5

Urea

0,45
0,4

Ammonium
nitrate

0,35

GJ/t

0,3

Stabilized
ammonium
nitrate

0,25
0,2
0,15
0,1
0,05
0

GJ/t fertilizer

GJ/t N

Fig.14. Cumulative exergy (GJ/t) of the emissions


from nitrogen fertilizers production

H3PO4 in
waste water

0,01
0,009
0,008
0,007
0,006
GJ/t
phosphoric acid 0,005
(100% P2O5) 0,004
0,003
0,002
0,001
0

HF in waste
water
HF in vents

Lower limit

Upper limit

Fig. 15. Chemical exergy of the emissions to air and to water


from wet process phosphoric acid production (as 100% P2O5)

H2O

0,3

F (as HF)
0,25

Phosphates
(as H3PO4)

0,2
GJ/t
(100% P2O5) 0,15
0,1
0,05
0
Liquid effluents

Gaseous emissions

Fig. 16. Chemical exergy of the emissions and polutants


from wet process phosphoric acid production (as 100% P2O5)

0,8

CaSO4.2H2O

0,7
0,6

F as CaSiF6

0,5
GJ/t
(100% P2O5) 0,4

Phosphate (as
3Ca3(PO4)2.CaF2)

0,3
0,2
0,1
0
Phosphogypsum

Fig. 17. Chemical exergy of major components


of waste phosphogypsum
from wet process phosphoric acid production (as 100% P2O5)

Example: Treatment of process steam and/or condensates


from ammonium nitrate production plant
Total exergy of the emissions from the process and from
the waste flows treatment
Exergy of the additional emissions, arising as a result of
the waste flows treatment process
Total net reduction of the exergy of the emissions as a
result of the waste flows treatment with recycling of the
pollutants back into the process
Exergy and cumulative exergy consumption of natural
resources in some processes of the waste flows treatment

Emissions to atmosphere and liquid effluents


from ammonium nitrate production*
Absorption
column with
ammonium
nitrate solution

Vacuum
evaporation
system

Gaseous emissions
and liquid effluents

Pollutant

Concentration

Process steam
before treating

NH3
NH4NO3

ppm w/w

3000-5000

Process condensate
before treating

NH3
NH4NO3

ppm w/w

1000-1200

Process steam and/or


condensate after treating

NH3
NH4NO3

ppm w/w

*In this work are used data from:


Bouilloud, P, Boujnah, N., INTEGRATION OF THE AN SOLUTION
PREPARATION AND TREATMENT OF PROCESS STEAM AND/OR
CONDENSATES, Fertilizer Focus, December, 1997, 40-43

<100
<100

0
<10

Total net reduction of the exergy of the emissions


as a result of the waste flows treatment
with recycling of the pollutants (NH3 + NH4NO3)
back into the ammonium nitrate production process
Reduction of
the emissions
from
production of
ammonium
nitrate,
ammonia and
nitric acid

Absorption
column with
ammonium
nitrate solution
Emissions
reduction

total
kg/t
NH4NO3

Two stage
vacuum
evaporation
system

Exergy
reduction
MJ/t
NH4NO3

Emissions
reduction

total
kg/t
NH4NO3

Three stage
vacuum
evaporation
system

Exergy
reduction
MJ/t
NH4NO3

Emissions
reduction

total
kg/t
NH4NO3

Vacuum
evaporation
system with
mechanical
compressor

Exergy
reduction
MJ/t
NH4NO3

Emissions
reduction

32,97

total
kg/t
NH4NO3

Exergy
reduction
MJ/t
NH4NO3

Emissions
reduction total

5,81

31,89

5,89

32,97

5,89

5,89

32,97

Additional
emissions

7,63

3,50

48,25

22,10

46,61 21,350 14,96

6,85

Total net reduction of natural gas and power exergy


consumption as a result of the waste flows treatment
with recycling of the pollutants (NH3 + NH4NO3)
back into the ammonium nitrate production process
Reduction of
the exergy in
production of
ammonium
nitrate,
ammonia and
nitric acid

Exergy
consumption
reduction total
Additional
exergy

Absorption column
with ammonium
nitrate solution

Two- and three


stage vacuum
evaporation system

Vacuum evaporation
system with
mechanical
compressor

Exergy
MJ/t
NH4NO3

Exergy
MJ/t
NH4NO3

Exergy
MJ/t
NH4NO3

63,1412

65,2508

65,2508

22,4832

14,0849

73,4611

Total net reduction of cumulative energy and cumulative


exergy consumption as a result of the waste flows treatment
with recycling of the pollutants (NH3 + NH4NO3)
back into the ammonium nitrate production process
Reduction of the
cumulative energy and
cumulative exergy
consumption
in production of
ammonium nitrate,
ammonia
and nitric acid

Absorption column
with ammonium
nitrate solution

Two- and three


stage vacuum
evaporation
system

Vacuum evaporation
system with
mechanical
compressor

Cumulative Cumulative Cumulative Cumulative Cumulative


energy
exergy
energy
exergy
energy
MJ/t
MJ/t
MJ/t
MJ/t
MJ/t
NH4NO3
NH4NO3
NH4NO3
NH4NO3
NH4NO3

Reduction of total
cumulative energy and 61,0007 139,6048 63,0402 144,2723 63,0402
exergy consumption

Cumulative
exergy
MJ/t
NH4NO3

144,2723

Additional cumulative
energy and cumulative 138,3166 65,3753 85,5239 41,4870 271,0746 288,8800
exergy consumption

CONCLUSIONS
An attempt is made to estimate the environmental impact
of mineral fertilizers production by the Second-Law
based indices.
The following exergy indices are found to be useful and
representative :
I. The chemical exergy of the pollutants and of the
emission flows, (referred to an unit of product), could be
used to compare different production processes and
different methods for emission abatement with respect to
their total environmental impact.
II. The exergy consumption and the cumulative exergy
consumption for the emissions abatement could be used
to compare different methods for emission abatement.
III. In the cases of the emission treatment with recycling of
the pollutants back into the process,
- the exergy of the additional emissions,
- the total exergy of the emissions from the process

University Prof. Assen Zlatarov


8010 Bourgas, Bulgaria
www.btu.bg