INTRODUCTION
In the ammonia synthesis, nitrogen is combined with hydrogen in a stoichiometric ratio of 1:3 to
give ammonia. Ammonia itself is used as a fertilizer. About 85% of ammonia consumptions used
for the manufacture of fertilizer. Air contains 79% (volume) of nitrogen. So, nitrogen needed for
the reaction can be obtained for air. The difficulty lies in separating the hydrogen needed for the
reaction from its source.
Most of the improvements in the technology regarding the ammonia synthesis over the past four
decades were concerned with the hydrogen production step. The major hydrogen sources are
natural gas, naphtha and coal. Most of the steam reforming plants use natural gas as feed stock.
Natural gas contains fewer impurities, high hydrogen to carbon ration and less percentage of
higher hydrocarbons. So natural gas is economical when compared with other feed stocks.
1
1.2 Properties of Ammonia:
Structural Properties:
Property Name Characteristic
Molecular shape Trigonal pyramid
Dipole moment 1.42 D
Physical Properties:
Property Characteristic
Molecular Formula NH3
Molecular weight 17.036 g/ mol
Specific gravity Gas 0.587 and Liquid 0.682
Boiling point -33.3°c
Freezing point -77.7°c
Density 0.86 kg/ m3 (at 1.013 bar & at boiling point)
Nature Alkaline
Color Colorless
Odor Strong pungent odor
Solubility Highly soluble in cold water (89.9 gm/ 100 ml at
0°c)
Auto ignition temperature 651°c
Basicity (pKb) 4.75 (reaction with water)
Critical temperature 133°c
Critical pressure 5 kg/ cm2
Viscosity of saturated liquid 0.25 cp at -15°c
Thermal conductivity of saturated 0.502 m °K at 0°c
liquid
2
1.3 Applications of Ammonia:
• Mainly used as fertilizer and refrigerant.
• In the pulp and paper industry for the pulping of wood.
• As a corrosion inhibitor in petroleum refineries
• In rubber production for the stabilization of natural and synthetic latex to prevent
coagulation.
• A chemical used in water plant for regeneration of weak base anion resins IRA-93.
• In the food and beverage industry as a source of nitrogen required for the growth of
yeast and micro-organism
• It is used for making ice, large scale refrigeration plants, air-conditioning units in
buildings and plants
3
CHAPTER-2
LITERATURE REVIEW
Characteristics of a Technology:
• Flexible
• Energy Efficient
• Economics
By considering all conditions Natural Gas & Naphtha is suitable. For Ammonia production
NFCL is using Haldor Topsoe steam reformation process.
4
2.1. Different types of Production Processes
5
2.1.2. Cyanamide Process
10000C
CaC2 (Calcium carbide) + N2 CaCN2 (Calcium Cyanamide) + C
10000C
CaCN2 (Calcium Cyanamide) + 3H2O (Steam) CaCO3 + 2NH3
The process was relatively simple, and capital costs were low. But it consumes large amounts of
electrical energy to make carbide. It is just a laboratory process. It leads to environmental effect
i.e. producing unwanted gases.
Purified water is used as feed stock in electrolysis process. H2 thus obtained is mixed with
required N2 from A.S.U. (Air Separation Unit) to get synthesis mixture. Byproducts of
electrolysis process are O2 and heavy water that have use in other industries.
The total energy requirement is 10200 KWH/ MT of ammonia. The plants based on this
process are located where low cost hydroelectricity is available. Electrolysis produces very pure
hydrogen for use in the electronics, pharmaceutical and food industries.
It is well established commercial technology. Competitive with SMR only where oil and/or
natural gas are expensive. Coal could replace natural gas and oil as the primary feedstock for
hydrogen production, since it is so plentiful in the world. It leads to environmental effect i.e.
producing unwanted gases.
6
2.1.5. Steam Reforming (Fossil fuel reforming)[7]
It is usually carried out in two stages using primary and secondary reformers. Desulfurized
naphtha or NG (Natural Gas) is subjected to steam reforming at about 28-30 kg/cm2 pressure and
around 800°C temperature in the primary reformer consisting of a large number of centrifugally
cast, high temperature, vertical alloy steel tubes packed with nickel catalyst. The overall reaction
is endothermic and requires large amount of heat. The gas leaving the primary reformer
containing 5-15% CH4 is sent to an auto thermal secondary reformer. The required amount of N2
is fed to secondary reformer through addition of air to give desired 3:1 H2 to N2 ratio in the
synthesis gas. Here CH4 is converted to H2, CO, CO2 over a single bed of catalyst.
The CO content of the gas is converted to CO2& H2 by passing over catalyst in the presence
of steam. Thus generating H2 by water gas shift reaction and is carried out in two stages. The
first stage high temperature (HT) shift conversion, is carried over iron-Cr catalyst at 350-430°c,
while the second stage, low temperature (LT) shift conversion, is carried over Cu based catalyst
at 200-280°c. In the HT shift conversion, level of CO is reduced from 12% to around 3% and in
the LT shift conversion, the CO level is reduced to around 0.2%. The process gas after shift
conversion, containing over 18% CO2 and less than 1% CO undergoes further purification in
CO2 removal section.
The purified synthesis gas mixture from containing N2& H2 in the mole ratio of 1:3 is
reacted at elevated temperature of the order of 450-500°c and 150-250 kg/cm2 pressure over an
activated iron catalyst 20-30% per promoted with potassium and alumina. The gas cooled first by
heat exchanger and finally by refrigeration to condense ammonia as liquid. Conversion of
synthesis gas to NH3 is about pass. The gas remaining after ammonia condensation is recycled to
the converter. The inert gases built up in the synthesis gas are purged. This was most common
method of producing hydrogen used in the industrial synthesis of ammonia. It is the least
expensive method. High temperature process (700 – 1100 °C).Nickel based catalyst (Ni).Produce
essentially pure hydrogen.
The cost of hydrogen production by reforming fossil fuels depends on the scale at which it is
done, the capital cost of the reformer and the efficiency of the unit, so that whilst it may cost
only a few dollars per kilogram of hydrogen at industrial scale, it could be more expensive at the
smaller scale needed for fuel cells. Fossil fuel reforming does not eliminate carbon dioxide
7
release into the atmosphere but reduces the carbon dioxide emissions as compared to the burning
of conventional fuels due to its increased efficiency.
8
2.2. Selection of the process
Steam reforming from natural gas (See figure 2.1) or other light hydrocarbons process is
selected because it involves high hydrogen to carbon ratio in ammonia synthesis reactor. And
compare to other methods mentioned, steam reforming process produces more hydrogen. The
process of gasification and partial oxidation involves extra air separation plant for production of
oxygen and nitrogen. But steam reforming process doesn’t require any air separation plant for
nitrogen. In gasification and partial oxidation operations involves high temperatures and
pressures, economically these involves high cost. But in steam reforming process involves less
temperatures and pressures compare to gasification and partial oxidation process.
Moreover, we get high yield in steam reforming process than partial oxidation and
gasification. For these reasons we can select the steam reforming process for production of
ammonia.
9
CHAPTER-3
MATERIAL BALANCE
Basis: 1250 tons/day
N2 + 3H2 ↔ 2NH3
By stoichiometry,
Basis: 1hr
If ‘X’ kgmol of Natural gas supplied then the H2 content as based on the natural gas composition
is given by
= 2.976X
10
From Reaction 1, 2.976X = 4595.58
Desulfurization: [9]
Here sulfur removal takes place and sulfur would be less than 3ppm
Desulfurizer
Assumption: The removal sulfur quantity is very minute and it is neglected from the statistics.
Primary Reformer:
11
N2 1.24 19.148 28 536.15
Assumption: Most of the industries are taking carbon to steam ratio as 1:3
Assumptions:
From reaction 1:
12
H2 produced = 3×1048.299 = 3144.87 kmol
From reaction 2:
From reaction 3:
From reaction 4:
CO + H2O → CO2 + H2
13
The total H2 produced from primary Reformer is:
From reaction 1:
Assumption: There won’t be any effect of reactions 2, 3 and 4 in the Secondary reformer.
From reaction 5:
CO + H2O → CO2 + H2
14
H2O Consumed = 450.33 kmol
Total H2O consumed in the Secondary Reformer = 314.48 + 450.33 = 764.81 kmol
Shift Converter:
CO + H2O → CO2 + H2
15
Low temperature converter:
CO + H2O → CO2 + H2
CO inlet = 60 kmol
CO2Absorber:
Methanator:
Assumptions: Here we have low CO, CO2 percentage compared to N2, H2 .So here we taken
100% conversion. So,
From reaction 1:
From reaction 2:
17
H2O formed = 2×27.84 = 55.68 kmol
N2 + 3H2 → 2NH3
1mol N2 → 3 mol H2
? ← 5424.23 mol H2
N2 1808.07 25.12
H2 5424.23 74.56
Reactor
Feed Product
Purge
5% inerts.
Recycle 1
18
Moles of N2 and H2 enter to the reactor is = 7251.4 + x kmol
23.18 = 0.0625y
In steady state operation attained the inerts present in purge is equal to inerts present in fresh
feed supply.
0.0625y = 23.18
y = 370.88 kmol
Balance at point 1:
0.2x = 5430.24
x = 27151.2 kmol
19
Summary:
R = 27151.2 kmol
Air 2062.116 _ _
20
CHAPTER 4
ENERGY BALANCE
The reactions involved are:
= 196104353 kJ/kmol
(kJ/kmol K)
6 N2 19.148 31.3762
Qin = ṁCp∆T
= {(1497.57×64.093)+(15.6×109.578)+(3.55×157.35)+(1.69×51.09)+(4632.63×38.9194)
+ (19.148×31.3762)}× (823-298)
= 146.6×106 kJ/hr
21
Table 4.2 Primary reforming section outlet flow rates
(kJ/kmol K)
1 H2 3901.82 30.8
2 N2 19.148 32.539
3 CO 436.04 32.965
Qout = {(3901.82×30.8)+(19.148×32.539)+(436.04×32.965)+(654.1×53.75)+(449.27×74.07)
+(2888.39×41.753)}×(1063-298)
= 248.018×106 kJ/hr
Secondary Reformer:
22
Table 4.3 Secondary reforming section outlet flow rates
(kJ/kmol K)
3 CO 300 33.94
5 H2 5294.77 31.51
6 N2 1827.218 33.56
Qout = [(134.78×81.1)+(2123.58×44.25)+(300×33.94)+(1104.43×55.83)+(5294.77×31.51)+
(1827.218×33.56)]×(1273-298)
= 394.77×106 kJ/hr
Qp = Qout-Qin + ∆H
Q = [(134.78×81.1)+(2123.58×44.25)+(300×33.94)+(1104.43×55.83)+(5294.77×31.51)
+(1827.218×33.56)] × (1000-350)
= 227.29×106 kJ
Q = ṁ(Cp∆T +λs)
∴ ṁ = 4900.7 kmol/hr
23
High Temperature Shift Conversion Inlet:
(kJ/kmol K)
3 CO 300 30.88
5 H2 5294.77 29.37
6 N2 1827.218 30.426
Qin = [(134.78×52.124)+(2123.58×36.619)+(300×30.88)+(1104.43×48.3035)+(5294.77×29.37)
+(1827.218×30.426)]×(623-298)
= 116.83×106kJ
(kJ/kmol K)
3 CO 60 31.223
24
4 CO2 1344.43 49.3873
5 H2 5534.97 29.58
6 N2 1827.218 30.755
Q = 367316.4557×(420-200) = 80.80×106 kJ
Q = ṁ(Cp∆T +λs)
∴ ṁ = 1742.19 kmol/hr
(kJ/kmolk)
3 CO 60 30.138
25
5 H2 5534.97 28.974
6 N2 1827.218 29.7504
(kJ/kmol K)
1 CH4 134.78 47
3 CO 12 30.238
5 H2 5582.97 29.025
6 N2 1827.218 29.837
Q = Qou t- Qin + ∆H
Q = [(134.78×47+(12×30.28)+(1392.97×45.6245)+(5582.97×29.025)+(1827.218×29.837)]
×(220-100) = 34.417×106 k
26
Absorber outlet:
Here Only CO2 was removed
Methanator Inlet:
(kJ/kmol K)
2 H2O 12 30.587
3 CO 27.84 47.226
4 H2 5582.97 29.2
5 N2 1827.218 30.149
27
Table 4.9 Methanator Outlet flow rates
(kJ/kmol K)
2 CO 0 30.789
3 CO2 0 47.9626
4 H2 5423.61 29.315
5 N2 1827.218 30.3336
(kJ/kmol K)
1 N2 1827.218 29.542
2 H2 5424.23 28.88
3 Ar 23.18 20.8614
28
Q = ṁCp∆T
= {(1827.218×29.542)+(5424.23×28.88)+(23.18×20.8614)}×(423-298)
= 26.39×106 kJ/hr
(kJ/kmolk)
2 Ar 23.18 20.8614
Qout = {(3440.26×48.1267)+(23.18×20.8614)+(370.88×30.347)}×(743.15-298)
=78.90×106 kJ/hr
29
CHAPTER-5
Heat Exchangers
Transfer of heat from one fluid to another is an important operation for most of the
chemical industries. The most common application of heat transfer is in designing of heat
transfer equipment for exchanging heat from one fluid to another fluid. Such devices for efficient
transfer of heat are generally called Heat Exchanger. Heat exchangers are normally classified
depending on the transfer process occurring in them.
The principal types of heat exchanger used in the chemical process and allied industries
1. Double-pipe exchanger: the simplest type, used for cooling and heating.
3. Plate and frame exchangers (plate heat exchangers): used for heating and cooling.
4. Plate-fin exchangers.
8. Agitated vessels.
9. Fired heaters.
30
Figure 5.1. Classificaton of heat exchangers depending on their applications.
31
5.1 Plate and frame heat exchangers[11]
This exchanger consists of a series of thin plates normal to the direction of flow of the fluids.
The plates provide a large surface area for heat exchange and are, at some places, more
convenient than the shell and heat tube exchanger primarily because of its unique shape.
The shell and tube exchanger is by far the most commonly used type of heat-transfer equipment
used in the chemical and allied industries. The advantages of this type are
5. Easily cleaned.
32
Essentially, a shell and tube exchanger consists of a bundle of tubes enclosed in a cylindrical
shell. The ends of the tubes are fitted into tube sheets, which separate the shell-side and tube-side
fluids. Baffles are provided in the shell to direct the fluid flow and support the tubes. The
assembly of baffles and tubes is held together by support rods and spacers.
Fixed tube-sheet exchanger (non-removable tube bundle): The simplest and cheapest type of
shell and tube exchanger is with fixed tube sheet design. In this type of exchangers the
tube sheet is welded to the shell and no relative movement between the shell and tube bundle
is possible .
Removable tube bundle: Tube bundle may be removed for ease of cleaning and replacement.
Removable tube bundle exchangers further can be categorized in floating-head and U-tube
exchanger.
Floating-head exchanger: It consists of a stationery tube sheet which is clamped with the
shell flange. At the opposite end of the bundle, the tubes may expand into a freely riding
floating-head or floating tube sheet. A floating head cover is bolted to the tube sheet and the
entire bundle can be removed for cleaning and inspection of the interior.
U-tube exchanger: This type of exchangers consists of tubes which are bent in the form of a ‘U’
and rolled back into the tube sheet. This means that it will omit some tubes at the centre of the
tube bundle depending on the tube arrangement. The tubes can expand freely towards the ‘U’
bend end.
33
Figure 5.2.. Floating
Floating- head heat exchanger(non-pull through type)
34
CHAPTER 6
HEAT EXCHANGER DESIGN
Solution:
Ammonia: Water:
Heat
Exchanger
Water Ammonia
inlet 293 K
outlet 313 K
By heat balance:
Q = ṁp∆T
c
at average temperature (t)300.5 K = 4.187 kJ/Kg.K
) ×4.187× (308-293)
16.24×1.991× (-313 + 405) = (
∴ 2 = 47.36 kg/sec
35
∆ ∆
LMTD = ∆ = !" = 48.76
∆ #
, , ( *(
+ = = = 0.133
- % & '(
For these values, LMTD correction factor FT = 0.87, (LMTD)C = 0.87×48.76 = 42.42 k
d0 = 25.4 mm = 0.25×10-1 m2
di = 0.221×10-1 m2
Tube length = 16 ft
Tube side:
36
Density = 996.4 kg/m3, thermal conductivity (K) = 0.359 W/m.K
= 0.04 m2
< = < ;)
aT = × (d1)2× = × (22.1×10-3)2×
& > & ;
Velocity:
m &.(;
a T ρT . &×;.&
v = = = 1.18 m/sec
Heat transfer coefficient (hi) = 173.5 × (K÷di) = 173.5× (0.359÷0.0221) = 2818.9 W/m2k
hi corrected :
hi (tw - 305.5) = U (T - t)
∴ tw = 312.028 = 39.02 0C
37
Tube Side pressure drop:
S U W×E×E
∆Ps = (Np×8×Jf× ((P ) (U )-0.14 + 2.5) ×
T V
U -0.14
≈1)
UV
we know(( )
Shell side:
R );.&
9] W .)(*× . (
Velocity = = = 5.79 m/sec de = 0.02508 m
38
_` E ).)×&.*× . )
Z .)'
Pr = = = 0.77
a] Pb
Z
Nu = = 0.023×Re0.8×Pr0.3
E &.*× . ) 0.14
UV
= 870W/m2K
. )
hs corrected = hs× = 140.1046× ( )
). * &.* . (×'.*×'.*
. ' * .;&*
= 8×0.025× × × ×0.8
= 17.445 Kpa
Finally, Calculation of ij
) ) ) &(.(×*
0k
= l + l = &(.(p*
m# o
Uc = 633.95 W/m2K
39
Summary
UC (corrected) 644.95
UD (assumed) 344
Rd Calculated 0.00132
Rd Required 0.0005
2.85 Allowable ∆v 10
40
CHAPTER 7
Mechanical Design
Shell and tube heat exchanger [9]
The minimum information required for the mechanical design of some important components
of shell and tube exchanger is summarized below:
Shell side and tube side passes: 1 shell pass and 6 tube passes.
Number, type, size, and layout of tubes: Number of tubes 612; tube length 4.87 m as per IS
4503 – 1967 and IS 2844 – 1964 standards; tube OD 25.4 mm; tube ID: 22.1 mm; square
pitch (Pt) = 1.25d0, floating head tube sheet.
Shell diameter and head: Shell ID 1080 mm; torispherical head is selected; carbon steel for
both shell and head.
Corrosion allowance: corrosion allowance of 3 mm for carbon steel is taken as per IS:4503
(10% greater than the highest process fluid temperature is taken); design pressure1.1×0.49
( 0.54) N/mm2 (10% higher than the inlet pressure of both the streams).
= 9.23 mm
41
II . Tori spherical head
It is most widely used in chemical industries for operating pressure up to 200 psi
)~
) * ) *
= 1080 − {d1080 − f d1080 + f + (2 × 64.8)}
= 144 mm
Leff = Lt + 2×hi
= 4.87 + 2×144×10-3
= 5.158 m
Thickness of head
v $Q
a = +
2 − 0.2 × v
)
= & 3 + O T = 1.77 for ri = 0.06×Ri
T
a = 7.13
42
III. Channel cover thickness
) v
=
10
C1 = 0.3
) √ .(×'.;
= ) ) .;
= 13.76mm
v
% =
3
0.785
=1− for square pitch
v
-
= 0.5
1 × 1080 5.6
% =
3 0.5 × 10.26
= 37.6 mm
43
RV &.(;
§¨© .ª×#.#
×;
• Water velocity, (vw) = = = 1.29 m/sec
W
ª ª
= 6.9 mm
¬ ® − ¯
= = 1.09
¬ ® − ¯( + 1)
P = Design pressure
m = gasket factor
e± e²±
Gasket width =
44
¬
= 1.09
¬
e± pe²±
Mean Gasket diameter (G) = = 1130 mm
(IX) Bolts :
µ
= (2×3.14×2.5×1130×3.75×0.54) + ( & ×11302×0.54) = 574808.41 N
M16 naminal thread diameter with bolt circle dia (Cb) of 860 mm, 44 bolts
µ
= & ×182×44 = 11190.96 mm2
45
¹º »º )) .;×) .;
ᴨᴦ¬ ×ᴨ×'.('×))(
The minimum gasket width Nmin = = = 30 mm
Flange thickness:
¾º À )); )
hD = = = 35 mm
W = Wm2 = 57808.4 N
HT = H - HD = 541277-503635.59 = 37642 N
46
Summation of moments and under operating condition
Mf = MD + M T + M G
ÁÂ Ã 9
tf =
w À À
, K= , A = Cb + 2E, E = 20
)); p( ) )
) )
K= = = 1.1 mm
Y = 18
tf =
) ) ' ×)*
) .;×)
= 55.95 mm
47
CHAPTER 8
Results and Discussions
1. Floating tube sheet allows for differential thermal expansion between the shell and the
tube bundle. Both the tube bundle and the shell side can be inspected and cleaned
mechanically. Fixed tube has no provision to allow for differential thermal expansion
developed between the tube and the shell side. This can be taken care by providing
expansion joint on the shell side.
U-tube: Because of U-bend some tubes are omitted at the centre of the tube bundle, tubes
can be cleaned only by chemical methods. Due to U-tube nesting, individual tube is
difficult to replace.
2. Triangular and rotated square patterns give higher heat transfer rates. But high pressure
drop in triangular pitch than square pitch.
3. Baffles: Baffles are used in the shell to create turbulence and so improve the rate of
transfer. Baffle space should be taken between 0.25Ds to Ds only. First trail was done with
baffle space 0.25Ds due to close baffle spacing pressure drop that is obtained for shell side
is 56 psi, which is too larger than allowable pressure drop. Then second trail was done
with baffle space 0.5Ds then the pressure drop obtained for shell side is 4.29 psi which is
also exceeding the allowable pressure drop. Next trail was taken with baffle space 0.6Ds
then obtained pressure is 2.5psi. It is an allowable pressure drop so that the baffle space
fixed as 0.6Ds.This was happen because of baffle spacing (effect the velocity of shell side
fluid). By increasing baffle spacing, pressure drop will reduce and vice versa.
4. Tube side Passes: Trail was taken as two passes the obtained pressure drop for tube side
is 0.25 psi, which is very low. So that tube passes need to be increased for better heat
transfer within the allowable pressure. Next trail taken as 4 passes, Pressure drop
obtained is 1.78 psi it is also very lower than allowable pressure. Next trail taken 6
passes, pressure drop obtained is 5.43 psi it is an acceptable pressure drop. Next trail was
done for 8 passes; Pressure drop obtained here is exceeding the allowable pressure drop.
So 6 tube passes taken for design. By increasing the tube passes the velocity of tube side
fluid will increase this results increase in pressure drop.
48
REFERENCES
1. Alwyn Pinto, “Ammonia production process”, EP0093502 B2, (17 Nov 1988).
2. David M. Himmelblau, James B. Riggs, “Basic Principles and Calculations in Chemical
Engineering”, 7th ed., University of Texas, (2004).
3. Erik Andreas Gam, “Process and reactor for the preparation of ammonia”, EP1123899
B1, (13 Oct 2004).
4. Martyn S. Ray and David W. “Johnston, Chemical Engineering Design Project A Case
Study Approach”, vol-6, 1989.
5. Peters, Max S. and Timmerhaus, Klaus D., “Plant Design & Economics”, 4th ed., McGraw Hill,
Inc. (1991).
6. Sarabjit S. Randhava, Surjit S, Randhava, Todd Harvey, Richard L. Kao, “Process for producing
ammonia from biomass”, W02010022106A3, (14 May 2010).
7. Speth Christian, “Process and converter for the preparation of ammonia”, WO2000026139 A1,
(11 May 2000).
8. Indian Standard (IS: 4503-1967): Specification for Shell and Tube Type Heat
Exchangers, BIS 2007, New Delhi.
9. R. K. Sinnott, Coulson & Richardson’s Chemical Engineering: Chemical Engineering
Design (volume 6), Butterworth-Heinemann, 3rded. 1999.
10. D. Q. Kern, Process Heat Transfer, McGraw-Hill Book Company, Int. ed. 1965.
11. Dutta B.K. „Heat Transfer-Principles and Applications‟, PHI Pvt. Ltd., New
Delhi,1sted. 2006.
12. James R. Couper; W. Roy Penney, James R. Fair, Stanley M. Walas, Chemical Process
Equipment: selection and design, Elsevier Inc., 2nd ed. 2005.
49