Literature-view of Ammonia-production

Block diagram of Ammonia production

Sulfur Steam Secondary Shift

Removal Reforming Reforming Conversion

Ammonia Synthesis Methanation CO2

Conversion Gas Removal
compress

Ammonia Ammonia Ammonia

Purification Transfer Storage

Primary Reforming:
Partial reforming of the hydrocarbons present in the purified gas is carried out in this
section by the use of heat and steam. Primary reformer has two sections.
 Convection Section
 Radiant Section
In the convection section the desulfurized gases are mixed with steam and after
preheating in the mixed feed coil in the convection section of the primary reformer the
mixture is then distributed to the catalyst tubes suspended in the radiant section of the
primary reformer. The vertical tubes are packed with a metallic Nickel catalyst and the
reforming reaction temperature is 820oC. medium pressure steam is provided here at
350oC and at a pressure of 40Kg/Cm3.
 Secondary Reformer:
The secondary reformer is a refractory lined vessel packed with a metallic nickel
catalyst.
Compressed air and the steam which has been pre heated in the convection section of
primary reformer are introduced into the process gas and the mixture is burnt here. This
rises the temperature sufficiently high for further reforming to take place. Also air
provides sufficient nitrogen for the conversion reaction of ammonia to take place at later
stages of the process.
Secondary reforming taking place here will reduce the methane contents to 0.3-0.4%.
the reaction over nickel bed is strongly heat absorbing and the temperature of gases
leaving is only around 1000oC.

High Temperature Shift Converter:

Here in the first reactor, the carbon monoxide content is reduced to 3.1 % over a
catalyst of Reduced Iron at 370˚C. The reaction is exothermic and outlet temperature of
gas is about 430˚C.

Low Temperature Shift Converter:

Gas enters the low temperature shift reactor at 242˚C and leaves at 255˚C. This
converter uses Copper catalyst. Since the catalyst is very sensitive towards sulfur
compounds, so it is protected by a guard bed of Zinc Oxide in the reactor top section.
The carbon monoxide content is reduced here to about 0.5%.

CO2 Removal
• There are many processes for the carbon dioxide removal and the one chosen here is
the CATACARB system.
• Most of CO2 is removed by its absorption in potassium carbonate solution in an
absorber.
• Here the carbon dioxide content, which has now risen to 17.5 %, is reduced to 0.1 %.
• The gas is first cooled down, saturated with water and carbon dioxide removal is carried
out in two absorption stages, by counter current contacting the gas with catacarb
solution in a packed bed absorber. The catacarb solution flows downwards by gravity
while the gas flow upwards through the tower.
• The catacarb solution consists of an aqueous solution containing the equivalent of 25%
potassium carbonate which combines chemically with carbon dioxide.
• The “rich” catacarb solution, from the bottom of the absorber is regenerated by, flashing
under low pressure into stripping tower and by heating. The carbon dioxide is driven off
and the regenerated catacarb solution from the bottom of stripping tower is returned to
the top of absorber for re-use.

Methanator:
The catalyst used for ammonia conversion is very sensitive to the oxides of carbon but
the raw synthesis gas still contains a small percentage (0.6%) of carbon monoxide
which was not oxidized in the shift reaction, and a small percentage (0.1%) of carbon
dioxide which was not removed by catacarb solution. These gases are now removed by
reaction with hydrogen to form methane and steam over a Nickel catalyst.

Gas Compression:
For conversion to ammonia the pressure is required to be high. So in order to bring the
synthesis gas up to reaction pressure it is necessary to compress it up to 147 kg/cm 2.
this is carried out in two case barrel type compressors.
In the first case, the raw synthesis gas is compressed from 26 kg/cm2 up to 70.4 kg/cm2.
it is then cooled to 8˚C and enters the second casing where it is compressed to 154
Kg/cm2

Ammonia converter:
This is highly exothermic reaction which takes place over a Reduced Iron catalyst which
has been modified by Aluminum, Potassium and Magnesium Oxides.
 Material Balance Calculations
Basis for calculations= 1Kgmol/hr
Primary Reformer:

D=3916kgmol/hr E=?

Primary Reformer

S=6525kgmol/hr
Reactions involved:
CH4 + H2O CO + 3H2 40% Conversion
CH4 + 2H2O CO2 + 4H2 60% Conversion
C2H6 + 2H2O 2CO + 5H2 100% Conversion

Balance stream Calculations for D:

component kgmol/hr mol%= mol- mass flow mass mol.wt=Kg
v/v% frac rate=Kg mass%=w frac /Kgmol
/hr /w%
H2 167.9964 4.3 0.043 335.99 0.053951 0.00053 2
28 474 9515
N2 724.8516 18.39 0.183 20295. 3.258970 0.03258 28
9 8448 847 9708
CH4 2720.836 69.6 0.696 43533. 6.990300 0.06990 16
8 3888 053 3001
C2H6 7.4404 0.16 0.001 223.21 0.035841 0.00035 30
6 2 888 8419
CO2 295.2664 7.54 0.075 12991. 2.086123 0.02086 44
4 7216 656 1237
Ar 0.3916 0.01 0.000 15.272 0.002452 2.45234 39
1 4 34 E-05
Total D 3916.783 100 1 622768 100 1 159
2 .5288
Balance stream Calculations for S:
compon Kgmol/ mol%=v/ mol-frac mass flow ma mol.wt=Kg/K
ent hr v% rate=Kg mass%=w/ ss gmol
/hr w% frac
H2O 6525.6 100 1 117462. 100 1 18
7 06
Total S 6525.6 100 1 117462. 100 1 18
7 06
Balance stream Calculations for E:
component Kgmol/h mol%= mol- mass flow mass mol.wt=K
r v/v% frac rate=K mass%= frac g/Kgmol
g/hr w/w%
H2 8345.81 68.962 0.6896 16691. 12.4165 0.1241 2
18 03028 20303 6236 3903 6539
N2 724.851 5.9894 0.0598 20295. 15.0976 0.1509 28
6 99786 94998 8448 415 76415
CH4 653.000 5.3957 0.0539 10448. 7.77205 0.0777 16
832 91833 57918 01331 1912 20519
C2H6 0 0 0 0 0 0 30
CO2 1274.76 10.533 0.1053 56089. 41.7239 0.4172 44
7648 49479 34948 77651 7582 39758
Ar 0.3916 0.0032 3.2358 15.272 0.01136 0.0001 39
35818 2E-05 4 0809 13608
CO 1103.21 9.1159 0.0911 30890. 22.9784 0.2297 28
552 47486 59475 03456 3092 84309
total E 12102.0 100 1 134430 100 1
39 .5652
Secondary Reformer:

E=12102kgmol/hr F=?
Secondary Reformer

H2 % 68.96203028
N2% 5.989499786
CH4% 5.395791833
C2H6% 0 A = 2448.7
CO2% 10.53349479 kgmol/hr
Ar% 0.003235818
CO% 9.115947486

Reaction Involve:
CH4 + O2 CO + H2O + H2 80% Conversion

Balance sheet for inlet-air in Secondary Reformer:

compon Kgmol/ mol%= mol-frac mass flow mas mol.wt=Kg/
ent hr v/v% rate=Kg/ mass%=w s Kgmol
hr /w% frac
O2 514.23 21 0.21 16455.6 23.30097 0.23 32
815 208 129 301
N2 1934.5 79 0.79 54166.4 76.69902 0.76 28
149 172 871 699
Air 2448.7 100 1 70622.0 100 1
5305 38
Balance sheet for outlet-stream in Secondary Reformer:
Added compon Kgmol mol% mol- mass flow mass mol.wt=
component ent /hr =v/v% frac rate=Kg/ mass% frac Kg/Kgm
%ages hr =w/w% ol
68.9620302 H2 9651. 62.90 0.629 19303.6 9.7750 0.0977 2
8 81346 87730 08773 2693 87399 50874
4 8 1
5.98949978 N2 2659. 17.33 0.173 74462.2 37.706 0.3770 28
6 3665 32694 33269 62 65076 66508
7 5
5.39579183 CH4 130.6 0.851 0.008 2089.60 1.0581 0.0029 16
3 00166 22824 51228 2662 45639
4 5 2
0 C2H6 0 0 0 0 0 0 30
10.5334947 CO2 1274. 8.308 0.083 56089.7 28.403 0.3 44
9 76764 70478 08704 7651 0804
8 3 8
0.00323581 Ar 0.391 0.002 2.552 15.2724 0.0077 0.0000 39
8 6 55237 38E- 3373 7
8 05
9.11594748 CO 1625. 10.59 0.105 45517.2 23.049 0.24 28
6 61618 54720 95472 532 30207
6 4
100 total F 15342 100 1 197477. 100 1
.5555 7937
6

High-Temperature Shift Convertor:

F=15342kgmol/hr G=?
HTSC
H2 % 62.90877308
N2% 17.33326947
CH4% 0.851228245
C2H6% 0
CO2% 8.308704783
Ar% 0.002552378
CO% 10.59547204
Reaction Involve:
CO + H2O CO2 + H2 60% Conversion
Balance sheet for outlet-stream in HTSC:
compon Kgmol/ mol%=v mol-frac mass flow mas mol.wt=Kg/
ent hr /v% rate=Kg/ mass%=w s Kgmol
hr /w% frac
H2 9913.0 65.6775 0.6567754 19826.0 10.37170 0.07 2
138 4468 47 2759 091
N2 2659.3 17.6193 0.17 74462.2 38.95386 0.3 28
665 3007 62 035
CH4 130.60 0.86527 0.0023 2089.60 1.093145 0.00 16
0166 6538 2662 549 24
C2H6 0 0 0 0 0 0 30
CO2 1740.2 11.5296 0.13 76570.1 40.05656 0.48 44
303 9779 3321 283
Ar 0.0025 1.69105 0.000016 0.09954 5.20744E- 0.04 39
5238 E-05 2739 05
CO 650.24 4.30813 0.07 18206.9 9.524678 0.12 28
6474 4008 0128 285
total G 15093. 100 1 191155. 100 1
4598 0263

Low Temperature shift Convertor:

G=15903kgmol/hr H=?
LTSC
H2 % 65.67754468
N2% 17.61933007
CH4% 0.865276538
C2H6% 0
CO2% 11.52969779
Ar% 1.69105E-05
CO% 4.308134008

Reaction Involve:
CO + H2O CO2 + H2O 50% Conversion
Balance sheet for outlet-stream in LTSC:
component Kgmol/h mol%= mol- mass flow mass mol.wt=K
r v/v% frac rate=K mass%= frac g/Kgmol
g/hr w/w%
H2 9194.63 66.466 0.6646 18389. 10.8057 0.1 2
7389 43859 64386 27478 3137
N2 2659.36 19.224 0.19 74462. 43.7548 0.42 28
65 09908 262 0871
CH4 65.3000 0.4720 0.0026 1044.8 0.61393 0.003 16
832 42973 01331 6257
C2H6 0 0 0 0 0 0 30
CO2 1417.92 10.249 0.1 62388. 36.6602 37 44
5874 94016 73845 7922
Ar 1.8801E 1.3590 0.0125 0.0007 4.30859 0.0000 39
-05 9E-07 33238 E-07 0039
CO 496.274 3.5874 0.037 13895. 8.16524 0.08 28
0559 79056 67356 4009
total H 13833.5 100 1 170180 100 1
0392 .7509

CO2-Absorber:

H=13833Kgmol/hr I=?
CO2-Absorber
component Kgmol/hr mol%=v/v% mol-frac mass flow
rate=Kg/hr mass%=w/w%
H2 % 67.40327615
H2 9982.44371 74.96705037 0.749670504 19964.88742 17.83017736
N2% 17.95652645
N2 2659.3665 19.97154886 0.199715489 74462.262 66.50051713
CH4% 0.881836085
CH4 130.600166 0.980792833 0.009807928
CO2 Removel 2089.602662 1.866175616
C2H6% 0
C2H6 0 0 0 0 0
CO2% 10.19137866
CO2 15.0934598 0.113350217 0.001133502 664.1122308 0.593103212
Ar% 1.14183E-07
Ar 1.691E-05 1.26996E-07 1.26996E-09 0.000659509 5.88992E-07
CO% 3.566982531
CO 528.271093 3.967257593 0.039672576 14791.59059 13.21002609
total I 13315.7749 100 1 111972.4556 100
Balance sheet for outlet-stream in CO2-Absorber:
compo Kgmol/ mol%=v mol-frac mass flow mass mol.wt=Kg/
nent hr /v% rate=Kg mass%= frac Kgmol
/hr w/w%
H2 9982.4 74.9670 0.7496705 19964.8 17.83017 0.178 2
4371 5037 04 8742 736 302
N2 2659.3 19.9715 0.1997154 74462.2 66.50051 0.665 28
665 4886 89 62 713 005
CH4 130.60 0.98079 0.0098079 2089.60 1.866175 0.018 16
0166 2833 28 2662 616 662
C2H6 0 0 0 0 0 0 30
CO2 15.093 0.11335 0.0011335 664.112 0.593103 0.005 44
4598 0217 02 2308 212 931
Ar 1.691E 1.26996 1.26996E- 0.00065 5.88992E 5.89E 39
-05 E-07 09 9509 -07 -09
CO 528.27 3.96725 0.0396725 14791.5 13.21002 0.132 28
1093 7593 76 9059 609 1
total I 13315. 100 1 111972. 100 1
7749 4556

Methanator:

I=13315.77 J=?

Methanator
H2 % 74.96705037
N2% 19.97154886
CH4% 0.980792833
C2H6% 0
CO2% 0.113350217
Ar% 1.26996E-07
CO% 3.967257593

Reactions Involve:
CO + 3H2 CH4 + H2O 100% Conversion

CO2 + 4H2 CH4 + 2H2O 100% Conversion

Balance sheet for outlet-stream in Methanator:
component Kgmol/h mol%= mol- mass flow mass mol.wt=K
r v/v% frac rate=K mass%= frac g/Kgmol
g/hr w/w%
H2 8482.44 72.591 0.7259 16964. 16.9443 0.1694 2
3712 50052 15005 88742 8761 43876
N2 2659.36 22.758 0.2275 74462. 74.3722 0.7437 28
65 46575 84657 262 8424 22842
CH4 543.364 4.6500 0.0465 8693.8 8.68332 0.0868 16
5524 33591 00336 32839 7496 33275
C2H6 0 0 0 0 0 0 30
CO2 0 0 0 0 0 0 44
Ar 1.69105 1.4471 1.4471 0.0006 6.58712 6.5871 39
E-05 7E-07 7E-09 59509 E-07 2E-09
CO 0 0 0 0 0 0 28
total J 11685.1 100 1 100120 100 1
7478 .9829

Ammonia-Convertor:
Basis= 100kgmol-feed
k L
Ammonia Convertor

Reaction:

N2 + 3H2 2NH3
Balance sheet for inlet-stream in Ammonia-Convertor:
compon Kgmo mol%= mol-frac mass flow mass mol.wt=Kg/
ent l/hr v/v% rate=Kg/ mass%=w frac Kgmol
hr /w%
H2 65.65 65.65 0.6565 131.3 13.41356 0.134 2
272 136
N2 21.98 21.98 0.2198 615.44 62.87313 0.628 28
814 731
CH4 6.99 6.99 0.0699 111.84 11.42553 0.114 16
583 255
Ar 1.31 1.31 0.0131 51.09 5.219336 0.052 39
78 193
NH3 4.07 4.07 0.0407 69.19 7.068426 0.070 17
537 684
Total K 100 100 1 978.86 100 1

Balance sheet for outlet-stream in Ammonia-Convertor:

compo Kgmol/ mol%=v mol-frac mass flow mass mol.wt=Kg/
nent hr /v% rate=Kg mass%= frac Kgmol
/hr w/w%
H2 48.581 54.8345 0.5483459 97.162 9.933177 0.099 2
9287 29 684 332
N2 16.265 18.3589 0.1835893 455.425 46.55959 0.465 28
2 3909 91 6 539 596
CH4 6.99 7.88978 0.0788978 111.84 11.43375 0.114 16
8274 83 592 338
Ar 1.31 1.47862 0.0147862 51.09 5.223091 0.052 39
9848 98 825 231
NH3 15.449 17.4380 0.1743804 262.638 26.85037 0.268 17
3333 4992 99 6667 919 504
Total L 88.595 100 1 978.156 100 1
5333 2667

Total moles in exit stream= 88.59/100 kgmol of feed

 Energy-Balance Calculations
Primary Reformer:

∆Hg=8485.7MJ/hr ∆Hout=28770MJ/hr

Primary Reformer
∆Hs=1950.45MJ/hr

Qin=662516MJ/hr
Secondary Reformer:

∆Hin=21236MJ/hr ∆Hout=35158MJ/hr
∆Hair=2116MJ/hr Secondary Reformer

Q-removed= -3184982MJ/hr
High-Temperature Shift Convertor:

∆Hin=121305MJ/hr ∆Hout=14504MJ/hr
HTSC

Q-removed= -586021.8MJ/hr
Low-Temperature Shift Convertor:

∆Hin=4744.4MJ/hr LTSC ∆Hout=5379MJ/hr

Q-removed= -328383MJ/hr
CO2-Absorber:
∆Hg=537Mj/hr
∆Hin=1354.4MJ/hr CO2-Absorber ∆Hco2=.57MJ/hr

Q-removed= -818.38MJ/hr
Methanator:

∆Hin=5747.3MJ/hr ∆Hout=6389.MJ/hr
Methanator

Q-removed= -7469487.8MJ/hr
Ammonia-Convertor:

∆Hin=102.24MJ/hr Ammonia ∆Hout=174.9MJ/hr

Convertor

Q-removed= -9167.11MJ/hr
 Chemical Plant Design

Mid-Term Assessment
Task 1 Literature View
Task 2 Material Balance
Task 3 Energy Balance

Submitted to: Prof.Dr. Mehmood Saleem

Submitted by: Sehar Ishtiaq
RP15-CE18
Submission Date: 30-01-2019

Institute of Chemical Engineering and Technology,

University of the Punjab,Lahore
 Chemical Plant Design

Mid-Term Assessment
Task 1 Literature View
Task 2 Material Balance
Task 3 Energy Balance

Submitted to: Prof.Dr. Mehmood Saleem

Submitted by: Noor-e-Hira
RP15-CE10
Submission Date: 30-01-2019

Institute of Chemical Engineering and Technology,

University of the Punjab,Lahore
 Chemical Plant Design

Mid-Term Assessment
Task 1 Literature View
Task 2 Material Balance
Task 3 Energy Balance

Submitted to: Prof.Dr. Mehmood Saleem

Submitted by: Rutaba Kamran
RP15-CE14
Submission Date: 30-01-2019

Institute of Chemical Engineering and Technology,

University of the Punjab,Lahore