Ammonia
Ammonia
Ammonia
Contents
1 Introduction .........................................................................................................2
2 Components .........................................................................................................3
3 Process Description..............................................................................................5
4 Physical Properties...............................................................................................8
5 Chemical Reactions ..............................................................................................9
Reforming Unit.................................................................................................9
Carbon Monoxide Conversion ........................................................................... 12
Carbon Dioxide Removal ................................................................................. 13
Methanation Unit............................................................................................ 15
Synthesis Unit ............................................................................................... 16
6 Simulation Approaches.......................................................................................18
7 Simulation Results .............................................................................................20
8 Conclusions ........................................................................................................21
9 References .........................................................................................................22
Contents
1 Introduction
Usability features such as an Excel file which allows the user to collect
simulation results from the synthesis reactor.
1 Introduction
2 Components
The table below lists the components modeled in the ammonia plant model.
Component
ID
Type
Component name
Formula
NH3
CONV
AMMONIA
NH3
H2
CONV
HYDROGEN
H2
N2
CONV
NITROGEN
N2
CH4
CONV
METHANE
CH4
AR
CONV
ARGON
Ar
CO
CONV
CARBON-MONOXIDE
CO
CO2
CONV
CARBON-DIOXIDE
CO2
H2O
CONV
WATER
H2O
O2
CONV
OXYGEN
O2
C2H6
CONV
ETHANE
C2H6
C3H8
CONV
PROPANE
C3H8
N-BUTANE
CONV
N-BUTANE
C4H10
I-BUTANE
CONV
ISOBUTANE
C4H10
N-PENTAN
CONV
N-PENTANE
C5H12
I-PENTAN
CONV
I-PENTANE
C5H12
N-HEXANE
CONV
N-HEXANE
C6H14
N-HEPTAN
CONV
N-HEPTANE
C7H16
SULFUR
CONV
SULFUR-8-ATOMIC-GAS
S8
H2S
CONV
HYDROGEN-SULFIDE
H2S
H3O+
CONV
H3O+
H3O+
OH-
CONV
OH-
OH-
NH4+
CONV
NH4+
NH4+
NH2COO-
CONV
CARBAMATE
NH2COO-
HCO3-
CONV
HCO3-
HCO3-
CO3--
CONV
CO3--
CO3-2
NH4HCO3S
SOLID
AMMONIUM-HYDROGEN-CARBONATE
NH4HCO3
NH4HCO3
CONV
AMMONIUM-HYDROGEN-CARBONATE
NH4HCO3
Every component is not included in all the plant sections in order to keep the
model as simple as possible. The higher hydrocarbons (C2-C7) are only
included in the reformer section. The CO2 Removal section only includes ions
2 Components
and electrolytes. The synthesis and refrigeration sections only include the
components H2, N2, Ar, CH4, NH3 and H2O.
2 Components
3 Process Description
Ammonia is produced basically from water, air, and energy. The energy
source is usually hydrocarbons, thus providing hydrogen as well, but may also
be coal or electricity. Steam reforming of light hydrocarbons is the most
efficient route, with about 77% of world ammonia capacity being based on
natural gas.
3 Process Description
Ammonia plants using natural gas as a feedstock include the following units:
Natural Gas De
Desulfurization
The natural gas is delivered as dry gas containing a maximum of 40 ppm by
weight of sulfur, which is a poison for the reformer catalyst. The
desulfurization unit reduces the sulfur content to about 5 ppm by
hydrogenating it to hydrocarbons a
and
nd hydrogen sulfide and then absorbing
the hydrogen
ydrogen sulfide in zinc oxides.
3 Process Description
Reforming Unit
This unit contains two sections, one is primary reforming, and another is
secondary reforming. The desulfurized hydrocarbon feed is reformed to
hydrogen and carbon oxides in the presence of steam in the primary
reformer, and additionally with hot air in the secondary reformer. The
reformed gas contains about 0.3 vol% CH4.
Methanation Unit
Even small quantities of CO (0.1 vol%) and CO2 (0.3 vol%) are poisons for
the ammonia synthesis catalyst. Thus they are reacted to methane over a
nickel catalyst. The residual content of CO + CO2 is less than 10 ppm.
Synthesis Unit
The synthesis gas is pressurized by a centrifugal compressor to approximately
300 bar and hydrogen and nitrogen are catalytically converted to ammonia.
Tailgas Scrubbing
The ammonia in the purge gas from the ammonia unit is recovered in the
tailgas scrubbing unit and fed to a refrigeration unit. The treated purge gas is
used as fuel for the primary reformer. The building blocks offered in this
package do not model this section of the plant.
Refrigeration
The ammonia gas in the synthesis loop is liquefied by ammonia evaporation in
the ammonia chiller and discharged as feed to the urea process and to
ammonia storage. The building blocks offered in this package do not model
this section of the plant.
3 Process Description
4 Physical Properties
The binary interaction parameters of H2, N2, Ar and CH4 with ammonia
were modified in order to obtain accurate solubilities of these species in
ammonia, which is important for the synthesis and refrigeration sections.
The binary parameters of the air system (N2, O2, Ar) were modified in
order to enable an accurate simulation of the vapor-liquid equilibrium in
the nitrogen plant.
Electrolyte NRTL method and RK equation of state are used to compute liquid
and vapor properties respectively in the CO2 Removal Unit. The NRTL
parameters for electrolyte pairs were regressed against VLE data from Maurer
(1988) [1]. NH3 is selected as Henry-components to which Henrys law is
applied and the Henrys constants are specified.
4 Physical Properties
5 Chemical Reactions
Reforming Unit
The main reaction occurring in the reformer is the conversion of methane to a
mixture of CO, CO2 and H2:
CH 4 + H 2 O CO + 3H 2
(Endothermic)
(A-1)
CO + H 2 O CO 2 + H 2
(Exothermic)
(A-2)
The kinetics expression for Reaction A-1, the reforming reaction, (Moe and
Gerhard, 1965)[2] is as follows:
(A-3)
k 2 P3
2 H 2 CO 2 2
K 2 CH 4 H 2O
R 3
P
SS 379
SS 2
(A-4)
k 2 Ac
31720
7.912
460
(A-5)
The factor Ac, catalyst activity, is used in the model to give a reasonable
reactor performance for the methane conversion. It may be adjusted such
that reactor performance matches plant data. The equilibrium constant, K2,
with units of atm2, is equal to K1K3. Hyman (1967) [3]gives:
49, 435
K1 exp
30.707 atm 2
t 460
5 Chemical Reactions
(A-6)
exp
K 3 exp
8,240
t 460
K3
7,351.24
t 460
(A-7)
(A-8)
K 3=
(H 2 )(CO 2 )
(H 2O)(CO)
(A-9)
dP
= Pfact 0.04183 0.003292Z - 0.0000395Z 2
dz
(A-10)
Where,
Z:
P:
pressure (atm)
Pfact:
or:
(A-11)
The pressure drop expression has been implemented as a user pressure drop
Fortran subroutine of RPlug model. The Fortran subroutine is REFPD.
Since the net reaction in the primary reformer is endothermic, the heattransfer rate is critical to the rate of reaction in the tube. The heat-transfer
rate is determined by the tube inside and outside heat-transfer coefficients,
the flame temperature, and the gas temperature. The heat transfer from the
flame to the outside of the tube occurs primarily by radiation. Here an
outside heat transfer coefficient is defined for ease of calculation.
(A-12)
TW
htout T f htinT
htout htin
(A-13)
The flux is in units of BTU/hr/sq ft of inside tube area. The htin and htout are
the inside and outside heat-transfer coefficients in units of BTU/hr/F/ft2 of
inside tube-wall area. Both coefficients vary with gas temperature T. The
inside heat-transfer coefficient is an overall physical coefficient determined
10
5 Chemical Reactions
only by the properties of the fluid. Beck (1962) gave the following correlation
for estimating htin:
htin
DP
kf
= 0.4 2.58 Re p
Prp
1/ 3
1/ 3
0.094 Re p
Prp
0.8
0.8
(A-14)
Hyman (1967) reported that the factor 0.4 is needed to account for the
smaller value of htin when ring-shaped catalyst is used instead of the pellets
used by Beck. The calculation of the thermal conductivity kf, viscosity, and
heat capacity were taken from Mok (1982).
The heat-transfer rate outside the tube is assumed to be governed by a
radiant heat-transfer mechanism:
Flux
Dout
Din
(A-15)
where Din and Dout are the inside and outside diameters of the tube, c is the
product of the Stefan-Boltzman constant and the effective emissivity, Tf,r and
Tw,r are the flame temperature and tube-wall temperature in degrees Rankine.
The heat transfer rate was implemented as user heat transfer Fortran
subroutines of RPlug model. The Fortran subroutines are REFHT, KFORMC,
HTCOEF, TWALL, BPARM, and RKEQ. Subroutines REFHT and KFORMC are
interface routines necessary to interface Aspen Plus RPlug model with other
Fortran subroutines developed by Mok (1982). HTCOEF computes the heat
transfer coefficient. TWALL computes the tube wall temperature. BPARM and
RKEQ are physical property routines used to compute transport properties
needed in HTCOEF and TWALL.
The primary reformer is generally represented by 1-3 RPlug reactors in series,
representing the number of firing zones of the unit in the plant. This allows
the fuel requirements of each fired zone to be calculated separately.
The fuel fed to the reformer contains hydrocarbons higher than methane,
whereas Equation (A-1) only represents the reforming of methane. These
higher hydrocarbons, however, are rapidly converted to methane and are
thus accurately modeled using a simple RSTOIC block prior to the reformer
tube with the following reactions:
3C 2 H 6 + H 2 O 5CH 4 + CO
(A-16)
3C 3 H 8 + 2H 2 O 7CH 4 + 2CO
(A-17)
(A-18)
(A-19)
(A-20)
(A-21)
(A-22)
5 Chemical Reactions
11
burner is equal to the heat absorbed in the reformer tubes. The combination
of the RPlug blocks for the reformer tubes and RSTOIC blocks for the burners
provides an accurate simulation of the reformer unit.
CO + H 2 O CO 2 + H 2
(A-23)
1/ 2
KF
Tref k LT YCOYH 2O 1- K 3
rco Ac
T P1 k AYCO k BYCO2
KF =
(A-24)
( Y CO 2 )( Y H 2 )
( Y CO )( Y H 2O )
(A-25)
where:
Ac
catalyst activity
kLT
K3
kA
kB
Tref
513.13K
temperature in K
temperature in F
atm-1
CO + H 2 O CO 2 + H 2
(A-26)
CO + H 2 O CO 2 + H 2
12
(A-27)
5 Chemical Reactions
Kf
K3
8240
KF=
(YCO2 )(YH2 )
(A-28)
(A-29)
(A-30)
(YCO )(YH 2O )
where:
Ac
catalyst activity
kHT
temperature in K
temperature in F
Equilibrium
2H 2 O H 3 O OH
(A-31)
Equilibrium
CO 2 2H 2 O H 3 O HCO 3
(A-32)
Equilibrium
HCO 3 H 2 O H 3 O CO 32
(A-33)
Equilibrium
NH 3 H 2 O NH 4 OH
(A-34)
Equilibrium
H 2 NCOO H 2 O NH 3 HCO 3
(A-35)
Salt
(A-36)
Dissociation
NH 4 HCO 3 NH 4 HCO 3
(A-37)
5 Chemical Reactions
13
EQUIL
NH 3 H 2 O NH 4 OH
(A-38)
EQUIL
2H 2 O H 3 O OH
(A-39)
EQUIL
HCO 3 H 2 O H 3 O CO 32
(A-40)
KINETIC
CO 2 OH HCO3
(A-41)
KINETIC
HCO3 CO 2 OH
(A-42)
KINETIC
NH 3 CO 2 H 2 O H 2 NCOO- H 3O
(A-43)
KINETIC
H 2 NCOO- H 3O NH3 H 2O CO 2
(A-44)
Salt
(A-45)
The equilibrium expressions for the reactions are taken from the work of Miles
et al.[6]. In addition, the power law expressions are used for the ratecontrolled reactions (reactions 4-7 in REA-NH3) and the general power law
expression is:
E 1 1 N
n
a
r k T T0 exp
C i i
R T T0 i 1
(A-46)
r kT n exp (
E N
a
) C i i
RT i 1
(A-47)
In this file, the reduced expressions are used. In equation A-47, the
concentration basis is Molarity, the factor n is zero, k and E are given in
Table 2. The kinetic parameters for reactions 4-7 in Table 3 are derived from
the work of Pinsent[7].
E (cal/mol)
4.32e+13
13249
2.38e+17
29451
1.35e+11
11585
4.75e+20
16529
The built-in Keq expression (Equation 3) is used for the salt precipitation
reaction of NH4HCO3,
ln K eq A B T C ln T DT
14
(A-48)
5 Chemical Reactions
The parameters A, B and C were regressed against SLE data from Trypuc et
al. [8].
-914.00821
38648.2117
136.174996
Methanation Unit
The methanation reactor, which removes trace amounts of CO from H2-rich
synthesis feed mixtures, is modeled as a plug flow reactor by RPlug.
Two reactions occur in the methanation reactor:
CO + 3H 2 CH 4 + H2O
(A-49)
CO 2 + 4H 2 CH 4 + 2H 2 O
(A-50)
APH0.5
P
2 CO
(A-51)
1 BPCO CPH0.5
2
A PCO
(A-52)
C 2 PH0.5
2
The data reported by Yadav and Rinker at 503, 513 and 529 K were fitted to a
simple Arrhenius equation as follows:
r 0.314e
1 1
1,300
T 513
P
CO
0.5
P
H 2
(A-53)
Proper modeling of the methanation must include the effect of the backward
reaction as equilibrium is approached. Hence, the complete version of
Equation A-53 is as follows:
r Ac 0.314e
5 Chemical Reactions
1 1
1,300
T 513
P
yCH 4 yH 2O
0.5 CO
3
2
yH
P
K
PH 2
CO
2
(A-54)
15
where, P is the pressure in kPa, y is the component mole fraction, KCO is the
equilibrium constant for Reaction A-49 and Ac is the catalyst activity factor.
K CO e
38.4523 26,270 / T
(A-55)
Kinetic data are not available for the methanation of CO2. We use the same
kinetic expression for CO2 as for CO, recognizing the weakness of this
approach, but also recognizing that the concentration of CO2 in the process
stream is very small. The rate of Reaction A-50 is given as:
r Ac 0.314e
K CO2 e
1 1
1,300
T 513
P
yCH 4 yH2 2O
0.5 yCO2 4 2
yH2 P K CO2
PH 2
(A-56)
33.923 21,621/ T
(A-57)
Synthesis Unit
The ammonia synthesis converter beds are modeled as a plug flow reactor by
RPlug.
The reaction stoichiometry considered is:
N 2 +3H 2 2NH 3
(A-58)
a 2A
2
AK aN keq a3
H kgmole
3
R Ac
2
m hr
aA
1 K a aWH
(A-59)
where:
Ac
catalyst activity
.654
1.523
and where keq is the equilibrium constant, AK, the specific rate constant, and
Ka, the adsorption equilibrium constant.
2001.6
2.6899
T
16
12104
T
(A-60)
(A-61)
(A-62)
5 Chemical Reactions
aN, aH, aA, in Equation (are the activities of nitrogen, hydrogen and ammonia.
and w are parameters. Nielsen also gave the following formula for
evaluating the activities:
P
Ai
Ci
0.5
0.5
ai xi P exp RT
Bi RT T 3 Ai xi Ai
(A-63)
where:
R
Pressure in atm
Temperature in K
xi
Ai
Bi
Ci
H2
0.1975
.02096
5.04 x 102
N2
1.3445
.05046
4.20 x 104
NH3
2.393
.03415
4.77 x 106
Ar
1.2907
CH4
2.2769
5 Chemical Reactions
17
6 Simulation Approaches
Comments / Specifications
Natural Gas
Desulfurization
Sep2 + RStoic
Reforming
RStoic + RPlug
Carbon Monoxide
Conversion
Carbon Dioxide
Removal
Flash2
Methanation
RPlug + Sep2
Synthesis
Refrigeration
Valve + HeatX
Spec (Target)
Manipulated Variables
F18
Purpose
RESULTS
18
6 Simulation Approaches
High
Temperature
Shift
Low
Temperature
Shift
Methanator
Synthesis
Converter
Kinetics
REFKIN
KFORMC
DRATE
HTKIN
KFORMC
LTKIN
KFORMC
MTHKIN
SYNKIN
KFORMC
RNH3
Pressure
Drop
REFPD
Heat
Transfer
REFHT
KFORMC
HTCOEF
TWALL
BPARM
RKEQ
Parameter
Default Value
REFKIN
R1 Catalyst activity
1.0
REFPD
1.0
REFHT
R1 Flame temperature
R2 Maximum tube temperature
R3 Radiative Heat transfer
coefficient
975C
1200C
1.9*10-8 kcal/hr/m2
HTKIN
R1 - Catalyst activity
1.0
LTKIN
R1 - Catalyst activity
1.0
MTHKIN
R1 - Catalyst activity
1.0
SYNKIN
R1 - Catalyst activity
1.0
6 Simulation Approaches
19
7 Simulation Results
Value
Unit
Feed
Process Air
53000
scmh
Natural Gas
32000
scmh
Process Stream
102041
kg/hr
Fuel to Furnace 1
10184
scmh
Fuel to Furnace 2
10854
scmh
Combustion Air
178220
scmh
BFW
170180
kg/hr
3101
kmol/hr
Product
20
7 Simulation Results
8 Conclusions
8 Conclusions
21
9 References
22
9 References