(1.4) & Chap 2&3 Full

1.
4 MARKET ANALYSIS:
The research done by Marina Shimonowa and Haley Rowe for FERTECON 2013 Ammonia
Outlook found that the world ammonia demand grew by 30.8 million tonnes over the period
from 2000 to 2010, roughly 3.1 million tonnes/year, equivalent to an average growth rate of
2.1% per year, driven in particular, by increasing demand for urea production and for use in
industrial applications. In the period 2021-2025 growth rates are expected to slow and be of
the order of 1.8 million tonnes/year. Demand for ammonia is predominantly driven by the
global demand for fertilizer. Out of nearly 175 million tonnes of ammonia consumed globally
in 2013, some 134.6 million tonnes was used in the production of fertilizer, equivalent to 77%
of global usage. A further 3% was applied directly into the ground as a fertilizer
(overwhelmingly in the United States). The remaining 19% - around 34 million tonnes was
used in a wide variety of industrial applications. (Marina Simonova, 2013)
Figure 1: Global Ammonia Demand. (Marina Simonova, 2013)
The bar chart above shown the most demand for ammonia comes from the production of
fertilizers. With the exception of China, where much of the ammonia produced is from coal
gasification, most of the worlds ammonia is produced from natural gas. Nitrogen fertilizer
consumption accounts for more than 80% of the world ammonia market, and with population
continuing to grow and no new arable land being developed, a renewed growth trend is
projected during the forecast period. Increased usage of nitrogen fertilizers, in particular
urea, will be required to meet the growing need for food. On a country-by-country basis,
nitrogen fertilizer use is closely related to the health and level of maturity of the agricultural
economy, disposable income and dietary changes.
The following pie chart shows world consumption of ammonia:
Figure 2: World consumption of Ammonia. (Chemical Economic Handbook: Ammonia)
World apparent consumption of ammonia increased by 18% during 20082013, although it

slowed during the latter part of 2008 and 2009. Growth is forecast at 2.7% annually during
20132018. Some regions will grow faster, in particular the United States, led primarily by
increased urea production. The global ammonia supply/demand balance is expected to move
from slightly tight to easing toward a surplus, provided at least half of the announced projects
come to fruition. However, if a majority of projects are delayed, the current tight situation
could persist. (Chemical Economic Handbook: Ammonia, Feb 2014).
Following a year of declining trend in ammonia prices during 2013 ammonia markets
stabilized by the end of January, with most benchmarks rebounding in February and firming
further in March. At the end of February spot sales in the Middle East were able to achieve
$458 fob netbacks, the same level as cfr Tampa price of $460 settled between Yara and
Mosaic in the middle of the month. By the 3rd week of March the Yuzhnyy price reached
$500 fob. The April contract settlement between Yara and Mosaic followed shortly after that
at a significant $120 increase reaching $580 cfr Tampa. This jump was an evidence of
several major supply disruptions in the global ammonia market since the start of 2014, which
tightened supply/demand balance to a degree when the buoyancy of ammonia prices
became very well pronounced. Additionally, an expectation of the upcoming spring demand
for direct application in the US rendered support to the bullish market sentiment. (Marina
Shimonowa).
Similar to any industrial process, ammonia manufacturing has undergone decades of
development to optimize production and reduce prices wherever possible. Many large-scale
plants across the world are built near natural gas reserves to reduce the cost of transporting
feedstock, but because of the centralization of plants in many countries, ammonia must be
transported to all corners of the country to satisfy agricultural needs. Currently, ammonia can
be sold from a factory at an average cost of $750/ton, but due to the process reliance on
natural gas, fluctuations in natural gas prices could significantly increase production costs for
ammonia manufacturing. Therefore, the cost of ammonia is susceptible to rapid change in
the event of a scarcity of natural gas, which is a fossil fuel of which an assumedly finite
amount is available. Subsquent fluctuations in ammonia price may have significant
consequences at larger scales, such as large farms limited by the increased cost of fertilizer.
Further research by Marina Shimonowa and Haley Rowe, they estimate that global ammonia
capacity will increase from approximately 225 million tonnes/year in 2013 to nearly 276
million tonnes/year by 2025, make it an increase of around 51 million tonnes/year. The
increase in ammonia capacity in the current decade from 2013-2025 is a reflection of the
major expansion plans for integrated ammonia/urea facilities and is expected to lead to
considerable oversupply in global urea markets in the medium-term until 2018/2019. Average
global utilisation rates for urea plants are expected to fall from the high levels in the period
from 2000 to 2012 of around 85% down to 70-75% in the period 2015-2020. Thereafter,
capacity growth is expected to slow through the rest of the forecast period in line with lower
growth rates for nitrogen fertilizer demand and the overhang of extensive capacity additions
in the decade 2010-2020. (Marina Simonova, 2013).
In Malaysia, most of ammonia projects presently popular around Sabah and Sarawak.
Petronas Chemical Fertilizer Sabah - A large-scale ammonia/urea project is to be established
by Petronas in Sabah and is included in our forecasts for start-up around mid-2015 the
company has said that the project is progressing well ahead of the October 2015 schedule.
The project comprises a 2,100 t/d (693,000 t/y) ammonia unit and 3,850 t/d (1.271 million t/y)
granular urea plant. There will be no export surplus of ammonia. In November 2012, the
South Korean company, Huchems, announced that it had signed a MOU with the
government of Sarawak province in Malaysia to build a 600,000 t/y ammonia plant and
downstream capacity for the production of 400,000 t/y of nitric acid and 200,000 t/y of
ammonium nitrate.
Therefore, we decide to run our ammonia plant with target capacity of 38,000 ton/year.
Whether this value will give us profit or bankruptcy will be discussed in profitability analysis
chapter. The target of our ammonia plant location will be in Malaysia (Sabah) and Indonesia.
CHAPTER 2.0
MATERIAL AND ENERGY BALANCE
2.1 MATERIAL BALANCE:
From the Haber' reaction equation:
*All the molar flowrate, molar fraction and temperature can be obtained from appendix*
2.1.1 Compressor (C-101)
Feed 1 Stream 2
T = 461.5
T = 26.7
total ,i total ,i = 226.79

= 226.79
N H3 x1 N H3 x1
, = 0.0000 , = 0.0000
CO2 x2 CO2 x2
, = 0.2000 , = 0.20001
N2 x3 N2 x3
, = 0.20001 , = 0.20001
i. Total material balance
Input = Output
Stream 1 = Stream 2
226.79 kmol/h = 226.79 kmol/h

ii. Material balance on component
a. Ammonia
Input = Output
0.000 (226.79) = 0.000(226.79)
0.0000 kmol/h = 0.0000 kmol/h
b. Carbon Dioxide
Input = Output
0.2000 (226.79) = 0.20001 (226.79)
45.36 kmol/h = 45.36 kmol/h
c. Nitrogen
Input = Output
0.20001 (226.79) = 0.20001 (226.79)
45.36 kmol/h = 45.36 kmol/h
d. Hydrogen
Input = Output
0.59999 (226.79) = 0.59998 (226.79)
136.07 kmol/h = 136.07 kmol/h

2.1.2 Mixer (M-101)
Stream 11
T = 27.4
total ,i = 2045.72
N H3 x1
, = 0.08906
CO2 x2
, = 0.17872
N2 x3
, = 0.13314
Stream 2 Stream 3
T = 66.7
T = 461.5

= 226.79
N H3 x1 N H3 x1
, = 0.0000 , = 0.08018
CO2 x2 CO2 x2
, = 0.20001 , = 0.18084
N2 x3 N2 x3
, = 0.20001 , = 0.13989
Input = Output
Stream 2 + Stream 11 = Stream 3
226.79 kmol/h + 2045.72 kmol/h = 2273.15 kmol/h
2272.51 kmol/h 2273.15 kmol/h

a. Ammonia
Input = Output
0.000 (226.79) + 0.08906(2045.72) = 0.08018(2273.15)
0 + 182.19 kmol/h = 182.26 kmol/h
182.19 kmol/h 182.26 kmol/h
b. Carbon Dioxide
Input = Output
0.20001 (226.79) + 0.17872 (2045.72) = 0.18084 (2273.15)
410.97 kmol/h 411.07 kmol/h
c. Nitrogen
Input = Output
0.20001 (226.79) + 0.13314 (2045.72) = 0.13989 (2273.15)
317.73 kmol/h 317.99 kmol/h
d. Hydrogen
Input = Output
0.59998 (226.79) + 0.59908 (2045.72) = 0.59909 (2273.15)
1361.62 kmol/h 1361.82 kmol/h

2.1.3 Heat exchanger (E-101)
Stream 3 Stream 4
T = 66.7 T = 482.2
total ,i = 2273.15
total ,i = 2273.15
N H3 x1 N H3 x1
, = 0.08018 , = 0.08018
CO2 x2 CO2 x2
, = 0.18084 , = 0.18084
N2 x3 N2 x3
, = 0.13989 , = 0.13989
Input = Output
Stream 3 = Stream 4
2273.15 kmol/h = 2273.15 kmol/h
a. Ammonia
Input = Output
0.08018 (2273.15) = 0.08018 (2273.15)
182.27 kmol/h = 182.27 kmol/h

b. Carbon Dioxide
Input = Output
0.18084 (2273.15) = 0.18084 (2273.15)
411.08 kmol/h = 411.08 kmol/h
c. Nitrogen
Input = Output
0. 13989 (2273.15) = 0.13989 (2273.15)
317.98 kmol/h = 317.98 kmol/h
d. Hydrogen
Input = Output
0.59909 (2273.15) = 0.59909 (2273.15)
1361.82 kmol/h = 1361.82 kmol/h

2.1.4 Packed Bed Reactor (R-101)
Stream 4 Stream 5
T = 482.2
T = 539.7
total ,i = 2273.15 total ,i

N H3 x1 = 5868.76
, = N H3 x1
, = 0.04561
0.08018
CO2 x2 CO2 x2
, = , = 0.69727
0.18084 N2 x3
, = 0.0469
Input = Output
Stream 4 Stream 5
2273.15 kmol/h 5868.76 kmol/h

a. Ammonia
Input = Output
0.08018 (2273.15) 0.04561 (5868.76)
182.27 kmol/h 267.69 kmol/h
b. Carbon Dioxide
Input = Output
0.18084 (2273.15) 0.69727 (5868.76)
411.08 kmol/h 4092.10 kmol/h
c. Nitrogen
Input = Output
0. 13989 (2273.15) 0.0469 (5868.76)
317.98 kmol/h 275.27 kmol/h
d. Hydrogen
Input = Output
0.59909 (2273.15) 0.21022 (5868.76)
1361.82 kmol/h 1233.7 kmol/h

Stream 5 Stream 6
T = 539.7
T = 26.7
total ,i = 5868.76 total ,i = 2187.74

N H3 x1 N H3 x1
, = 0.04561 , = 0.12236
CO2 x2 CO2 x2
, = 0.69727 , = 0.1879
N2 x3 N2 x3
, = 0.0469 , = 0.12583
Input = Output
Stream 5 Stream 6
5868.76 kmol/h 2187.74 kmol/h
a. Ammonia
Input = Output
0.04561 (5868.76) = 0.12236 (2187.74)
267.69 kmol/h = 267.69 kmol/h

b. Carbon Dioxide
Input = Output
0.69727 (5868.76) 0.1879 (2187.74)
4092.10 kmol/h 411.08 kmol/h
c. Nitrogen
Input = Output
0. 0469 (5868.76) = 0.12583 (2187.74)
275.27 kmol/h = 275.27 kmol/h
d. Hydrogen
Input = Output
0.21022 (5868.76) = 0.56392 (2187.74)
1233.7 kmol/h = 1233.7 kmol/h

2.1.6 Tower (T-101)
Stream 7
T = 26.70C
distillate, D = 2047.77 kmol/h
N H3 x1
, = 0.08906
CO2 x2
, = 0.17872
T-101
Stream 6 N2 x3
, = 0.13314
T = 26.70C
total,i = 2187.74 kmol/h
N H3 x1
, =
0.12236
CO2 x2
, =
0.1879 Stream 9
T = 26.70C
bottom, B = 139.97 kmol/h
N H3 x1
, = 0.60947
CO2 x2
, = 0.32225
N2 x3
, = 0.0188
Input = Output
Stream 6 = Stream 7 + Stream 9
2187.74 kmol/h = 2047.77 + 139.97 = 2187.74 kmol/h
a. Ammonia
Input = Output
0.12236 (2187.74) = 0.08906 (2047.77) + 0.60947 (139.97)
267.69 kmol/h = 182.38 + 85.31 = 267.69 kmol/h
b. Carbon Dioxide
Input = Output
0.1879 (2187.74) = 0.17872 (2047.77) + 0.32225 (139.97)
411.08 kmol/h = 365.97 + 45.11 = 411.08 kmol/h
c. Nitrogen
Input = Output
0.12583 (2187.74) = 0.13314 (2047.77) + 0.0188 (139.97)
275.27 kmol/h = 272.64 + 2.63 = 275.27 kmol/h
d. Hydrogen
Input = Output
0.56392 (2187.74) = 0.59908 (2047.77) + 0.04947 (139.97)
1233.7 kmol/h = 1226.77 + 6.93 = 1233.7 kmol/h

2.1.7 Splitter (SP-101)
Stream 10
T = 26.7
total ,i = 2045.72
N H3 x1
, = 0.08906
Stream 7 CO2 x2
, = 0.17872
T = 26.7
N2 x3
, = 0.13314
total ,i = 2047.77
N H3 x1
, =
Stream 8
0.08906
T = 26.7
CO2 x2
, =
0.17872 total ,i = 2.05 kmol/h
N H3 x1
, = 0.08898
CO2 x2
, = 0.1789
N2 x3
, = 0.13315
Input = Output
Stream 7 = Stream 8 + Stream 10
2047.77 kmol/h = 2.05 kmol/h + 2045.72 kmol/h
2047.77 kmol/h = 2047.77 kmol/h

a. Ammonia
Input = Output
0.08906 (2047.77) = 0.08898 (2.05) + 0.08906 (2045.72)
182.38 kmol/h = 182.38 kmol/h
b. Carbon Dioxide
Input = Output
0.17872 (2047.77) = 0.1789 (2.05) + 0.17872 (2045.72)
365.97 kmol/h = 365.97 kmol/h
c. Nitrogen
Input = Output
0.13314 (2047.77) = 0.13315 (2.05) + 0.13314 (2045.72)
272.64 kmol/h = 272.64 kmol/h
d. Hydrogen
Input = Output
0.59908 (2047.77) = 0.59897 (2.05) + 0.59908 (2045.72)
1226.77 kmol/h =1226.77 kmol/h

Stream 11
Stream 10
T = 27.4
T = 26.7

= 2045.72
N H3 x1 N H3 x1
, = , = 0.08906
0.08906
CO2 x2
CO2 x2 , = 0.17872
, =
0.17872 N2 x3
, = 0.13314
Input = Output
Stream 10 = Stream 11
2045.72 kmol/h = 2045.72 kmol/h
a. Ammonia
Input = Output
0.08906 (2045.72) = 0.08906 (2045.72)
182.20 kmol/h = 182.20 kmol/h
b. Carbon Dioxide
Input = Output
0.17872 (2045.72) = 0.17872 (2045.72)
365.60 kmol/h = 365.60 kmol/h
c. Nitrogen
Input = Output
0.13314 (2045.72) = 0.13314 (2045.72)
272.37 kmol/h = 272.37 kmol/h
d. Hydrogen
Input = Output
0.59908 (2045.72) = 0.59908 (2045.72)
1225.55 kmol/h = 1225.55 kmol/h
2.2 ENERGY BALANCE:

Table 2.2.1: References of Hf and Cp of each components. (Sources: Felder)
Cp(kJ/kg.K)
COMPONENTS Hf (kJ/kmol)
a b
Ammonia, NH3 -46.19 35.15e-3 2.954e-5
Carbon Dioxide, CO2 -393.5 36.11e-3 4.233e-5
Nitrogen, N2 0 29.00e-3 0.2199e-5
Hydrogen, H2 0 28.84e-3 0.00765e-5
Reference: NH3(g), CO2(g), H2(g) and N2(g) at 25oC and 1 atm

Component in out
(kmol/h) (kmol/h)
Ammonia, NH3 0.00 1 0.00 5
Carbon dioxide, CO2 45.36 2 45.36 6
Nitrogen, N2 45.36 3 45.36 7
Hydrogen, H2 136.07 4 136.07 8
T2
NH3 (26.7C) : 1=( f )NH + ( C P ) dT

3
T1
3
35.15 10
( +2.954 105 T )dT
1 = 26.7
(46.19 )+
25
= ( 46.19) + (0.06)
= 46.13 kJ/mol
CO2 (26.7C) :
2=( f )CO + CO (26.7 )
2 2
2 = (393.5 )+interpolation of
26.725
10025
=
[ T 0
2.90

] [ ]
= ( 393.5) + (0.0657)
= 393.43 kJ/mol
(*the interpolation is using Kramer's rule and its data can get from appendix*)
N2 (26.7C) :
3=( f ) N + N ( 26.7 )
2 2
3 = ( 0 ) +interpolation of
26.725
10025 [
=
T 0
2.190
] [ ]
= ( 0) + (0.04964)
= 0.04964 kJ/mol
H2 (26.7C) :
4 =( f )H + H (26.7 )
2 2
26.725
10025 [
=
T 0
2.160
] [ ]
= ( 0) + (0.04896)
= 0.04896 kJ/mol
T2
NH3 (461.5C) : 5=( f ) NH + ( C P ) dT

3
T1
3
35.15 10
( +2.954 105 T )dT
5 = 461.5
(46.19 ) +
25
= ( 46.19) + (18.479)
= 27.71 kJ/mol
CO2 (461.5C) :
6=( f )CO + CO (461.5 )
2 2
[ 461.5400
500400 ] [
=
T 16.35
21.3416.35]
= ( 393.5) + (19.42)
= 374.08 kJ/mol
N2 (461.5C) :
7=( f ) N + N (461.5 )
2 2
[ 461.5400
500400 ] [
=
T 11.15
14.2411.15]
= ( 0) + (13.05)
= 13.05 kJ/mol
H2 (461.5C) :
8=( f ) H + H (461.5 )
2 2
[ 461.5400
500400 ] [
=
T 10.89
13.8310.89]
= ( 0) + (12.6981)
= 12.698 kJ/mol
Component in out
(kmol/h) (kJ/mol) (kmol/h) (kJ/mol)
Ammonia, NH3 0.00 -46.13 0.00 -27.71
Carbon dioxide, CO2 45.36 -393.43 45.36 -374.08
Nitrogen, N2 45.36 0.04964 45.36 13.05
Hydrogen, H2 136.07 0.04896 136.07 12.698
Q =
= out out
= [(0)(-27.71) + (45.36)(-374.08) + (45.36)(13.05) +(136.07)(12.698)]
[(0)(-46.13) + (45.36)(-393.43) + (45.36)(0.04964) + (136.07)(0.04896)]
= -14648.50394 (-17837.07114)
= 3188.5672 kmol/hr x kJ/mol x 1000 mol/kmol
= 3188567.2 kJ/h
= 885.71 kJ/s @ kW
Therefore, the positive sign shows that the reaction is absorbing heat or known as
endothermic reaction.
2.2.2 Mixer (M-101)
Reference: NH3(g), CO2(g), H2(g) and N2(g) at 27.4oC and 1 atm

Component in out
(kmol/h) (kmol/h)
0.00 1 182.26 5
Ammonia, NH3
182.19 0 - -
45.36 2 411.07 6
Carbon dioxide, CO2
365.611 0 - -
45.36 3 317.99 7
Nitrogen, N2
272.367 0 - -
136.07 4 1361.82 8
Hydrogen, H2
1225.55 0 - -
H T current is equal to T ref

For stream 11, = 0 because
T2
NH3 (461.5C) : 1= ( C P ) dT
T1
3
35.15 10
( +2.954 105 T )dT
1 = 461.5

27.4
= 18.393 kJ/mol
T2
CO2 (461.5C) : 2= ( C P ) dT
T1
3
36.11 10
( +4.233 105 T )dT
2 = 461.5

27.4
= 20.167 kJ/mol
T2
N2 (461.5C) : 3= ( C P ) dT
T1
3
29.00 10
( +0.2199 105 T )dT
3 = 461.5

27.4
= 12.822 kJ/mol
T2
H2 (461.5C) : 4 = ( C P ) dT
T1
28.84 103
( +0.00765 105 T )dT
4 = 461.5

27.4
= 12.528 kJ/mol
T2
NH3 (66.7C) : 5= ( C P ) dT
T1
35.15 103
( +2.954 105 T )dT
5 = 66.7

27.4
= 1.436 kJ/mol
T2
CO2 (66.7C) : 6= ( C P ) dT
T1
36.11 103
( +4.233 105 T )dT
6 = 66.7

27.4
= 1.497 kJ/mol
T2
N2 (66.7C) : 7= ( C P ) dT
T1
29.00 103
( +0.2199 105 T )dT
7 = 66.7

27.4
= 1.144 kJ/mol
T2
H2 (66.7C) : 8= ( C P ) dT
T1
28.84 103
( +0.00765 105 T )dT
8 = 66.7

27.4
= 0.112 kJ/mol
Component in out
(kmol/h) (kJ/mol) (kmol/h) (kJ/mol)
Ammonia, NH3 0.00 18.393 182.26 1.436
Carbon dioxide, CO2 45.36 20.167 411.07 1.497
Nitrogen, N2 45.36 12.822 317.99 1.144
Hydrogen, H2 136.07 12.528 1361.82 0.112
Q = = out out
= [(182.26)(1.436) + (411.07)(1.497) + (317.99)(1.144) +(1361.82)(0.112)]
[(0)(18.393) + (45.36)(20.167) + (45.36)(12.822) +(136.07)(12.528)]
= 1393.40155 3201.066
= -1807.66445 kmol/hr x kJ/mol x 1000 mol/kmol
= -1807664.45 kJ/h = -502.129 kJ/s @ kW

Component in out
(kmol/h) (kmol/h)
Ammonia, NH3 182.26 1 182.27 5
Nitrogen, N2 317.99 3 317.98 7
Hydrogen, H2 1361.82 4 1361.82 8
T2
NH3 (66.7C) : 1=( f )NH + ( C P ) dT

3
T1
35.15 103
( +2.954 105 T )dT
1 = 66.7
(46.19 )+
25
= (-46.19) + (1.522)
= -44.668 kJ/mol
T2
CO2 (66.7C) : 2=( f )CO + ( C P ) dT

2
T1
3
36.11 10
( +4.233 105 T )dT
2 = 66.7
(393.5 ) +
25
= (-393.5) + (1.587)
= -391.91 kJ/mol
T2
N2 (66.7C) : 3=( f ) N + ( C P ) dT
2
T1
29.00 103
( +0.2199 105 T )dT
3 = (0) + 66.7

25
= (0) + ( 1.214)
= 1.214 kJ/mol
T2
H2 (461.5C) : 4 =( f )H + ( C P ) dT
2
T1
28.84 103
( +0.00765 105 T )dT
4 = 66.7
(0)+
27.4
= 1.203 kJ/mol
T2
NH3 (482.2C) : 5=( f ) NH + ( C P ) dT

3
T1
3
35.15 10
( +2.954 105 T )dT
5 = 482.2
(46.19 ) +
25
= ( 46.19) + (19.496)
= 26.694 kJ/mol
CO2 (482.2C) :
6=( f )CO + CO (482.2 )
2 2
[ 482.2400
500400 ] [
=
T 16.35
21.3416.35

]
= ( 393.5) + (20.45)
= 373.048 kJ/mol
7=( f ) N + N (482.2 )
N2 (482.2C) : 2 2
[ 482.2400
500400
= ] [
T 11.15
14.2411.15
]
= ( 0) + (13.689)
= 13.689 kJ/mol
H2 (482.2C) :
8=( f ) H + H (482.2 )
2 2
[ 482.2400
500400
=
] [
T 10.89
13.8310.89

]
= ( 0) + (13.306)
= 13.306 kJ/mol
Component in out
(kmol/h) (kmol/h)
Ammonia, NH3 182.26 -44.668:1.522 182.27 -26.694:19.496
Carbon dioxide, CO2 411.07 -391.91:1.587 411.08 -373.048:20.45
Nitrogen, N2 317.99 1.214 317.98 13.689
Hydrogen, H2 1361.82 1.203 1361.82 13.306
Q =
= out out
= [(182.27)(-26.694) + (411.08)(-373.048) + (317.98)(13.689) +(1361.82)(13.306)]

[(182.26)(-44.668) + (411.07)(-391.91) + (317.99)(1.214) +(1361.82)(1.203)]
= -135744.8821 (-167219.3241)
= -31474441.96 kJ/h
= -8742.90 kJ/s @ kW
Therefore, the negative sign shows that the reaction is releasing heat to the surrounding or
known as exothermic reaction.
2.2.4 Packed Bed Reactor (R-101)

Component in out
(kmol/h) (kmol/h)
Ammonia, NH3 182.27 1 = 0 267.69 5
Carbon dioxide, CO2 411.08 2 = 0 4092.10 6
Nitrogen, N2 317.98 3 = 0 275.27 7
Hydrogen, H2 1361.82 4 = 0 1233.70 8

T2
NH3 (539.7C) : 5= ( C P ) dT
T1
35.15 103
( +2.954 105 T )dT
5 = 539.7

482.2
= 2.889 kJ/mol
T2
CO2 (539.7C) : 6= ( C P ) dT
T1
36.11 103
( +4.233 105 T )dT
6 = 539.7

482.2
= 3.319 kJ/mol
T2
N2 (539.7C) : 7= ( C P ) dT
T1
29.00 103
( +0.2199 105 T )dT
7 = 539.7

482.2
= 1.732 kJ/mol
T2
H2 (539.7C) : 8= ( C P ) dT
T1
28.84 103
( +0.00765 105 T )dT
8 = 539.7

482.2
= 1.661 kJ/mol
Component in out
(kmol/h) (kmol/h)
Ammonia, NH3 182.27 0 267.69 2.889
Carbon dioxide, CO2 411.08 0 4092.10 3.319
Nitrogen, N2 317.98 0 275.27 1.732
Hydrogen, H2 1361.82 0 1233.70 1.661
Q = = out out
= [(267.69)(2.889) + (4092.10)(3.319) + (275.27)(1.732) +(1233.70)(1.661)]
[(182.26)(0) + (411.07)(0) + (317.99)(0) +(1361.82)(0)]
= 16880.92187 0
= 16880921.87 kJ/h
= 4689.145 kJ/s @ kW

Component in out
(kmol/h) (kmol/h)
Ammonia, NH3 267.69 1 = 0 267.69 5
Carbon dioxide, CO2 4092.10 2 = 0 411.08 6
Nitrogen, N2 275.27 3 = 0 275.27 7
Hydrogen, H2 1233.70 4 = 0 1233.70 8

T2
NH3 (26.7C) : 5= ( C P ) dT
T1
35.15 103
( +2.954 105 T )dT
5 = 26.7

539.7
= -22.324 kJ/mol
T2
CO2 (26.7C) : 6= ( C P ) dT
T1
36.11 103
( +4.233 105 T )dT
6 = 26.7

539.7
= -24.674 kJ/mol
T2
N2 (26.7C) : 7= ( C P ) dT
T1
29.00 103
( +0.2199 105 T )dT
7 = 26.7

539.7
= -15.196 kJ/mol
T2
H2 (26.7C) : 8= ( C P ) dT
T1
28.84 103
( +0.00765 105 T )dT
8 = 26.7

539.7
= -14.806 kJ/mol
Component in out
(kmol/h) (kmol/h)
Ammonia, NH3 267.69 0 267.69 -22.324
Carbon dioxide, CO2 4092.10 0 411.08 -24.674
Nitrogen, N2 275.27 0 275.27 -15.196
Hydrogen, H2 1233.70 0 1233.70 -14.806
Q = = out out
= [(267.69)(-22.324) + (411.08)(-24.674) + (275.27)(-15.196) +(1233.70)(-14.806)]
[(267.69)(0) + (4092.10)(0) + (275.27)(0) +(1233.70)(0)]
= -38568.0646 0
= -38568064.6 kJ/h
= -10713.35 kJ/s @ kW
2.2.6 Tower (T-101)

Component in out
(kmol/h) (kmol/h)
267.69 1=0 182.38 5
Ammonia, NH3
85.31 6
411.08 2=0 365.97 7
Carbon dioxide, CO2
45.11 8
275.27 3=0 272.64 9
Nitrogen, N2
2.63 10
1233.70 4=0 1226.77 11
Hydrogen, H2
6.93 12
T2
NH3 (26.7C) : 5=( f ) NH + ( C P ) dT

3
T1
35.15 103
( +2.954 105 T )dT
5 = 26.7
(46.19 )+
25
= ( 46.19) + (0.0611)
= 46.13 kJ/mol
T2
CO2 (26.7C) : 7=( f )CO + ( C P ) dT

2
T1
36.11 103
( +4.233 105 T )dT
7 = 26.7
(393.5 ) +
25
= ( 393.5) + (0.0632)
= 393.44 kJ/mol
T2
N2 (26.7C) : 9=( f ) N + ( C P ) dT
2
T1
29.00 103
( +0.2199 105 T )dT
9 = 26.7
(0)+
25
= ( 0) + (0.0494)
= 0.0494 kJ/mol
T2
H2 (26.7C) : 11=( f )H + ( C P ) dT
2
T1
28.84 103
( +0.00765 105 T ) dT
11 = 26.7
(0)+
25
= ( 0) + (0.0490)
= 0.0490 kJ/mol
Since Tcurrent is same for all the output stream;
Therefore,
5 = 6 = -46.13 kJ/mol
7 = 8 = -393.44 kJ/mol
9 = 10 = 0.0494 kJ/mol
11 = 12 = 0.0490 kJ/mol
Q = = out out
= [(182.38)(-46.13) + (365.97)(-393.44) + (272.64)(0.0494) +(1226.77)(0.0490)] +
[(85.31)(-46.13) + (45.11)(-393.44) + (2.63)(0.0494) +(6.93)(0.0490)]
[(267.69)(0) + (411.08)(0) + (275.27)(0) +(1233.70)(0)]
= -152326.3848 + (-21682.95921) 0
= -174009344 kJ/h
= -48335.93 kJ/s @ kW
known as exothermic reaction
2.2.7 Splitter (SP-101)

Component in out
(kmol/h) (kmol/h)
182.38 1=0 182.20 5
Ammonia, NH3
0.18 6
365.97 2=0 365.60 7
Carbon dioxide, CO2
0.37 8
272.64 3=0 272.37 9
Nitrogen, N2
0.27 10
1226.77 4=0 1225.55 11
Hydrogen, H2
1.23 12
T2
NH3 (26.7C) : 5=( f ) NH + ( C P ) dT

3
T1
35.15 103
( +2.954 105 T )dT
5 = 26.7
(46.19 )+
25
= ( 46.19) + (0.0611)
= 46.13 kJ/mol
T2
CO2 (26.7C) : 7=( f )CO + ( C P ) dT

2
T1
36.11 103
( +4.233 105 T )dT
7 = 26.7
(393.5 ) +
25
= ( 393.5) + (0.0632)
= 393.44 kJ/mol
T2
N2 (26.7C) : 9=( f ) N + ( C P ) dT
2
T1
29.00 103
( +0.2199 105 T )dT
9 = 26.7
(0)+
25
= ( 0) + (0.0494)
= 0.0494 kJ/mol
T2
H2 (26.7C) : 11=( f )H + ( C P ) dT
2
T1
28.84 103
( +0.00765 105 T ) dT
11 = 26.7
(0)+
25
= ( 0) + (0.0490)
= 0.0490 kJ/mol
Since Tcurrent is same for all the output stream;
Therefore,
5 = 6 = -46.13 kJ/mol
7 = 8 = -393.44 kJ/mol
9 = 10 = 0.0494 kJ/mol
11 = 12 = 0.0490 kJ/mol
Q = = out out
= [(182.20)(-46.13) + (365.60)(-393.44) + (272.37)(0.0494) + (1225.55)(0.0490)] +
[(0.18)(-46.13) + (0.37)(-393.44) + (0.27)(0.0494) + (1.23)(0.0490)]
[(182.38)(0) + (365.97)(0) + (272.64)(0) + (1226.77)(0)]
= -152173.043 + (-153.802592) 0
= -152326845.6 kJ/h
= -42313.01 kJ/s @ kW
Component in out
(kmol/h) (kmol/h)
Ammonia, NH3 182.20 1 182.20 5
Nitrogen, N2 272.37 3 272.37 7
Hydrogen, H2 1225.55 4 1225.55 8
T2
NH3 (26.7C) : 1=( f )NH + ( C P ) dT

3
T1
35.15 103
( +2.954 105 T )dT
1 = 26.7
(46.19 )+
25
= ( 46.19) + (0.0611)
= 46.13 kJ/mol
T2
CO2 (26.7C) : 2=( f )CO + ( C P ) dT

2
T1
36.11 103
( +4.233 105 T )dT
2 = 26.7
(393.5 ) +
25
= ( 393.5) + (0.0632)
= 393.44 kJ/mol
T2
N2 (26.7C) : 3=( f ) N + ( C P ) dT
2
T1
29.00 103
( +0.2199 105 T )dT
3 = 26.7
( 0) +
25
= ( 0) + (0.0494)
= 0.0494 kJ/mol
T2
H2 (26.7C) : 4 =( f )H + ( C P ) dT
2
T1
3
28.84 10
( +0.00765 105 T )dT
4 = 26.7
(0)+
25
= ( 0) + (0.0490)
= 0.0490 kJ/mol
T2
NH3 (27.4C) : 5=( f ) NH + ( C P ) dT

3
T1
35.15 103
( +2.954 105 T )dT
5 = 27.4
(46.19 ) +
25
= ( 46.19) + (0.0862)
= 46.10 kJ/mol
T2
CO2 (27.4C) : 6=( f )CO + ( C P ) dT

2
T1
3
36.11 10
( +4.233 105 T )dT
6 = 27.4
(393.5 ) +
25
= ( 393.5) + (0.0893)
= 393.41 kJ/mol
T2
N2 (27.4C) : 7=( f ) N + ( C P ) dT
2
T1
3
29.00 10
( +0.2199 105 T )dT
7 = 27.4
(0)+
25
= ( 0) + (0.0697)
= 0.0697 kJ/mol
T2
H2 (26.7C) : 8=( f ) H + ( C P ) dT
2
T1
3
28.84 10
( +0.00765 105 T )dT
8 = 27.4
( 0) +
25
= ( 0) + (0.0692)
= 0.0692 kJ/mol
Component in out
(kmol/h) (kmol/h)
Ammonia, NH3 182.20 -46.13 182.20 -46.10
Carbon dioxide, CO2 365.60 -393.44 365.60 -393.41
Nitrogen, N2 272.37 0.0494 272.37 0.0697
Hydrogen, H2 1225.55 0.0490 1225.55 0.0692
Q = = out out
= [(182.20)(-46.10) + (365.60)(-393.41) + (272.37)(0.0697) + (1225.55)(0.0692)]
[(182.20)(-46.13) + (365.60)(-393.44) + (272.37)(0.0494) + (1225.55)(0.0490)]
= -152126.3238 (-152173.043)
= 46719.249 kJ/h
= 12.98 kJ/s @ kW
CHAPTER 3.0
HEAT INTEGRATION
3.1 INTRODUCTION
Based on the onion model of process design, heat exchanger net works is the third step of
design procedures after synthesis of reactor system, separation and recycle system. The
main objective of energy integration is to recover the excess heat in the entire plant in order
to minimize the consumption of hot and cold utilities.
From the economic point of view, process heat integration is one of the effective ways to
reduce operating cost. This integration allows heat to transfer from hotter streams to the
streams that need to be heated up, by using various heat recovery equipments. At the first
glance, this approach seems to increase the number the heat exchangers. However, it is
more profitable to save operating cost rather than capital cost for a long-term industry.
A good initialization of heat integration is considering that no individual heat exchanger has
temperature differences smaller than T min for possible heat recovery. The next procedure is
to obtain a composite curve in order to determine the pinch temperature, minimum hot and
cold utilities by applying the Pinch Technology Method. This will be followed by the heat
exchanger network design to ensure maximum energy recovery. Finally, the energy
consumption, heat exchangers areas and units before and after energy integration will be
compared, and thus determine the total saving of the utilities.
3.2 PINCH ANALYSIS
Pinch technology is used to determine the amount of energy that can be recovered from a
plant, often with consideration for practical process constraints. The two most common
methods to calculate the amount of energy recovered using the pinch technology are through
plotting a composite curve or using the problem table analysis. The reason is to compare
results obtained from both methods. This is one way to reduce the error in calculations.
There are a few steps in performing a pinch analysis which are:
STEP 1 : Choose a Minimum Approach Temperature
This represents the smallest temperature difference that two streams leaving or entering a
heat exchanger can have and for this case, the temperature chosen is 20 . Typically,
the range is from 5 to 20 but not cast in concrete. Temperature approach is
important as it can differentiate the obtained result. The loads on the hot and cold utilities
increase as the minimum approach temperature increases. This will reduces the capital
investment but will increases the operating costs.
Table 3.0: Stream number of heat exchangers

INDICAT Cp, Cp
FLOWR
T T out
ION OF STREA CONDI (kJ/kg (kW/ Qavailable
ATE,
STREA M NO TION (C) (kW)
(C)
(kg/s) ) )
M
1 5 Hot 54.125 1.474 79.780 539.7 26.7 48860
2 3 Cold 9.125 2.618 23.889 66.7 482.2 5684
From overall stream table;
kJ kmol
Stream 3:
Cp=37.837 0.0692 =2.618 kJ /kg
kmol . kg
kJ kmol
Stream 5:
Cp=48.949 0.0301 =1.474 kJ /kg
kmol . kg
STEP 2 : Construct a Temperature Interval Diagram
All the process streams are represented by a vertical line in temperature interval diagram. At
the left-hand side, the hot streams which require cooling are drawn while at the right-hand
side, the cold streams which need heating are drawn. Each process stream is represented
by the vertical line with an arrow at the end indicating the direction of the temperature
change. The diagram is divided into temperature intervals by draw the horizontal lines
through the end of the lines.
Stream 1 2
Cp 1.474 2.678
T (C) T (C) Cp T
539.7 519.7 55.275
A
502.2 482.2 -500.262

B
86.7 66.7
C
88.44
26.7 6.7
Figure 3.0: Temperature Interval Diagram
Cp T ( A )=1.474 ( 539.7502.2 )=55.275 kW
Cp T ( A )=( 1.4742.678 ) ( 502.286.7 )=500.262kW
Cp T ( A )=1.474 ( 86.726.7 )=88.44 kW
STEP 3 : Construct a Cascade Diagram

HOT UTILITY
C
In the cascade diagram, the net amount of energy in each temperature interval is shown.
The excess energy can always be cascaded down to the next temperature level. This is
O
because energy can always be transferred down a temperature gradient. It is important to
highlight that excess energy cannot be transferred upward to a higher temperature interval
L
for system in which only thermal energy is being transferred. This obeys the second law of
thermodynamics- that transfer of energy up a temperature gradient is possible only if work is
done on the system.
D
A U
QC=88.
44
55.275
C
QH=444.
B987
TI
-500.262
88.44
55.275
LI
PI
PINCH a
N
C
H
-------------------------------------------------------------------------------------------------------------------------
b
Figure 3.1: The Cascade Diagram
From the cascade diagram above, it can be concluded as;
Pinch Temperature : Hot stream = 86.7C
Cold stream = 66.7C
Minimum Utilities : Hot Utility, QH = 444.987
Cold Utility, QC = 88.44
STEP 4 : Calculate the Minimum Number of Heat Exchangers
In order to find the minimum number of heat exchangers needed to carry out the heat
transfer for the minimum utility design, the step continues from step 3 to step 4. Once the
pinch point have been found, the heat transfer problem will be split into two, and above and
below the pinch will be considered as separate systems.
i. Above the Pinch
1 HU
667.722 444.987
667.722 444.987
1112.709
Minimum Number of Exchanger, Nmin = 2
ii. Exact Match Solution (Below the pinch)
88.44
CU Minimum Number of Exchanger, N min = 1
88.44
STEP 5 : Design the Heat Exchanger Network
i. Above the Pinch
Stream 1 2
Cp (kJ/kg.C) 1.474 2.678
482.2
2 QH=444.987
539.7 Q1=667.722 kW 316.04
1 1
86.7 66.7
ii. Exact Match Solution (Below the Pinch)
Stream 1
Cp (kJ/kg.C) 1.474
86.7 QC=88.44 kW
1
26.7
From above the pinch region, the minimum number of exchanger required is 2, which is the
same as initial number of exchanger used. Nevertheless, from below the pinch area, it can
be seen only one utility is needed to recover all the energy that has been transferred thus
required only one exchanger. Therefore, it fulfill the purpose of pinch analysis which is to
minimize the number of heat exchanger and utility used but maximize the energy recovery.
When the number of utility and exchanger required decrease, the cost of equipment also
decreases. Thus, the objectives are achieved.
3.3 PFD AFTER HEAT INTEGRATION
Figure 3.2: PFD After Heat Integration

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1.

Figure 1: Global Ammonia Demand. (Marina Simonova, 2013)

The following pie chart shows world consumption of ammonia:

Figure 2: World consumption of Ammonia. (Chemical Economic Handbook: Ammonia)

World apparent consumption of ammonia increased by 18% during 20082013, although it

MATERIAL AND ENERGY BALANCE

2.1 MATERIAL BALANCE:

From the Haber' reaction equation:

2.1.1 Compressor (C-101)

total ,i total ,i = 226.79

i. Total material balance

226.79 kmol/h = 226.79 kmol/h

0.000 (226.79) = 0.000(226.79)

0.0000 kmol/h = 0.0000 kmol/h

0.2000 (226.79) = 0.20001 (226.79)

45.36 kmol/h = 45.36 kmol/h

0.20001 (226.79) = 0.20001 (226.79)

45.36 kmol/h = 45.36 kmol/h

0.59999 (226.79) = 0.59998 (226.79)

136.07 kmol/h = 136.07 kmol/h

total ,i total ,i = 2273.15

i. Total material balance

Stream 2 + Stream 11 = Stream 3

226.79 kmol/h + 2045.72 kmol/h = 2273.15 kmol/h

2272.51 kmol/h 2273.15 kmol/h

0.000 (226.79) + 0.08906(2045.72) = 0.08018(2273.15)

0 + 182.19 kmol/h = 182.26 kmol/h

182.19 kmol/h 182.26 kmol/h

0.20001 (226.79) + 0.17872 (2045.72) = 0.18084 (2273.15)

45.36 kmol/h + 365.611 kmol/h = 411.07 kmol/h

410.97 kmol/h 411.07 kmol/h

0.20001 (226.79) + 0.13314 (2045.72) = 0.13989 (2273.15)

45.36 kmol/h + 272.367 kmol/h = 317.99 kmol/h

317.73 kmol/h 317.99 kmol/h

0.59998 (226.79) + 0.59908 (2045.72) = 0.59909 (2273.15)

136.069 kmol/h + 1225.55 kmol/h = 1361.82 kmol/h

1361.62 kmol/h 1361.82 kmol/h

i. Total material balance

2273.15 kmol/h = 2273.15 kmol/h

ii. Material balance on component

0.08018 (2273.15) = 0.08018 (2273.15)

182.27 kmol/h = 182.27 kmol/h

0.18084 (2273.15) = 0.18084 (2273.15)

411.08 kmol/h = 411.08 kmol/h

0. 13989 (2273.15) = 0.13989 (2273.15)

317.98 kmol/h = 317.98 kmol/h

0.59909 (2273.15) = 0.59909 (2273.15)

1361.82 kmol/h = 1361.82 kmol/h

total ,i = 2273.15 total ,i

i. Total material balance

2273.15 kmol/h 5868.76 kmol/h

0.08018 (2273.15) 0.04561 (5868.76)

182.27 kmol/h 267.69 kmol/h

0.18084 (2273.15) 0.69727 (5868.76)

411.08 kmol/h 4092.10 kmol/h

0. 13989 (2273.15) 0.0469 (5868.76)

317.98 kmol/h 275.27 kmol/h

0.59909 (2273.15) 0.21022 (5868.76)

1361.82 kmol/h 1233.7 kmol/h

total ,i = 5868.76 total ,i = 2187.74

i. Total material balance

5868.76 kmol/h 2187.74 kmol/h

ii. Material balance on component