Professional Documents
Culture Documents
Thermodynamic Estimation of The Environmental Impact of Mineral Fertilizers Production
Thermodynamic Estimation of The Environmental Impact of Mineral Fertilizers Production
urea
Liquid effluents:
Process condensate (from surplus steam): 0,1% NH3, 0,1% CH3OH
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
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
6 H3PO4 + 10 CaSO4.2H2O +2 HF
Liquid effluents:
Filtration waters: Phosphates and fluorides
Solid wastes:
Phosphogypsum CaSO4.2H2O
Why exergy ?
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
20.024
11.372
3.73
1.2192
2.4104
22.649
2.648
3.8544
0.4576
0.1501
0.0203
1.407
Gaseous emissions
and liquid effluents
Pollutant
NH3
urea
dust
mg/Nm3
8-13
12-110
NH3
14 g/Nm3
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
0,016
0,014
0,012
GJ/t urea
0,01
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
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
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
New plants
H2O in waste
water
H2O
0,7
NH3
0,6
CH3OH
0,5
N2+O2+H2O
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
Pollutant
Tail gas
before
treatment
NO
NO2
N2O
NOx
Tail gas after (as NO2)
N2O
treatment
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
0,09
0,08
0,07
0,06
0,02
0,01
0
Extended
absorption
SCR
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
0,25
NOx in tail gas
before treating
0,2
GJ/t HNO3
(100% )
0,15
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
Medium
pressure/High
pressure plant
with extended
absorption
Medium
pressure/High
pressure plant
with NSCR
4.970
6.644
5.049
0.441
2.151
0.594
Degree of Perfection, %
17.50
28.30
30.81
65.06
45.34
47.53
13.896
7.478
9.822
7.20
13.37
10.18
EXERGY INDICES
0,008
0,007
0,006
NH4NO3 in waste
water
0,005
GJ/t
ammonium 0,004
nitrate
0,003
0,002
0,001
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
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
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
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
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
NH3
NH4NO3
ppm w/w
<100
<100
0
<10
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
6,85
Exergy
consumption
reduction total
Additional
exergy
Absorption column
with ammonium
nitrate solution
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
Absorption column
with ammonium
nitrate solution
Vacuum evaporation
system with
mechanical
compressor
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