Final Report
Final Report
Change in enthalpy for the reactants going from 770K to 298K =
1- For methane= -11.92 MKCal
2- For Steam= -2.8 MKCal
Change in enthalpy for products going from 298K to 1054K=
1- For methane=5.15 MKCal
2- For steam = 31.45 MKCal
3- For H2 = 26.4 MKCal
4- For CO = 3.63 MKCal
5- For CO2 = 6.97 MKCal
= 118.55 MKCal
Calculation of energy released from fuel gas:
Net energy released from fuel gas = Heat of combustion of fuels Heat consumed by
flue gases to reach 1328k.
Calculation of heat of combustion:
1- Heat of combustion for methane = 191.7 Kcal/gm-mol
2- Heat of Combustion for H2 = 57.76 Kcal/gm-mol
3- Heat of combustion for C2H6 = 339.2 Kcal/gm-mol
4- Heat of combustion for C3H8 = 487.3 Kcal/gm-mol
Net Heat of Combustion = 179.58 MKCal
Heat Consumed in rise in temperature of flue gases =
Heat consumed = 54.9 + 16.2 + 11.43 + 1.31 19.1 - 3.42 0.27 4.52 MkCal
= 56.53 MKCal
NET HEAT RELEASED FROM FLUE GAS TO PRIMARY REFORMER = 179.58-56.53 MKC
NET HEAT TO PRIMARY REFORMER = 123.05 MKcal
Total number of burners = 576
Heat released per burner = 123.05/576 = 20920 Kcal/Hr
Calculation of efficiency of primary reformer radiant zone :
e =
e = 118.55/ 123.05 = 96.34 %
Secondary Reformer Analysis :
Inlet feed to Secondary reformer:
Component Volumetric Flow( NM3/HR) Percentage By Volume
Methane 19181 6.97
Steam 113641 41.34
Carbon-Monoxide 14726 5.35
Carbon-Dioxide 16362 5.95
Hydrogen 110972 40.37
Total Gas flowrate = 274882 NM3/HR
Dry gas flowrate = 161241 nm3/hr
Steam: Dry gas Ratio = 0.704
N2 in the exit of Secondary Reformer = 57388 NM3/Hr
Therefore Process Air entering the secondary reformer = 72643 NM3/Hr
Oxygen content in process air = 15255 Nm3/Hr
Combustion Zone analysis :
Considering higher affinity of combustion for H2 first we will consider combustion of H2 first.
O2 available for combustion = 15255 NM3/HR
H2 combusted = 30510 NM3/Hr
Heat released in combustion = 77.62 MKCal/Hr
Reforming Zone Analysis :
CH4 + 2 H2O CO2 + 4 H2 (1)
CO2 + H2 CO + H2O (2)
CH4 reacted in (1) = 18239 NM3/HR
% Conversion of CH4 = 95 %
CO formed in Reaction (2) = 16810 NM3/Hr
Analysis Of gas leaving secondary Reformer :
Component Flowrate(NM3/Hr) Percentage By Volume
Steam 124835 33.7
H2 136536 36.9
CO 31536 8.5
CO2 17937 369873 4.8
CH4 955.65 0.25
Ar 686.11 0.1
N2 57388 15.5
ENERGY ANALYSIS OF SECONDARY REFORMER :
For calculating the enthalpy balance in the secondary reformer for the reactants and products
we can the process in 4 parts to calculate net enthalpy change.
Entahlpy changes for part-1 :
1- N2 = -2.045 MKCal
2- O2 = -3.01
3- CO2 =- 6.62
4- CO = -3.63
5- H2 = -26.46
6- H2O = -31.49
7- CH4 = -8.37
Total = -81.625 MKCal/hr
Enthalpy changes for part-2 :
1- Heat evolved in combustion of H2 = -77.6 MKCal/Hr
2- Heat consumed in Reaction (1) = 31.65 MKCal/Hr
Primary Reformer exit
at 781 Deg Celcius
+
Process air at 558 Deg
Celcius
Reactants at 25
Deg Celcius
Products at
25 Degree
Celcius
Products at
980 Deg
Celcius
3- Heat consumed in Reaction (2) = 7.28 MKCal/Hr
Total = -38.67 MkCal/hr
Enthalpy changes for part-3:
1- N2 =10.09 MKCal
2- CO2 = 9.38
3- C0 =9.99
4- H2 = 41.58
5- H2O = 43.16
6- CH4 = 0.57
7- Ar = .06
Total = 114.83
-5.465 MKCal/Hr
Therefore heat lost in Secondary reformer = 5.465MKCal/Hr
HT SHIFT CONVERTOR ANALYSIS :
Shift Conversion Reaction :
C0 + H2O CO2 + H2 + heat
Heat of reaction = -9.846 Kcal/mol
CO Reacted = 24003 Nm3/Hr
Percentage Conversion of CO= 76.11 %
Shift convertor exit gas analysis:
Component Volumetric
Flowrate(NM3/Hr)
Percentage by vol
H2 160539 43.4
CH4 941 0.25
CO 7533 2.03
CO2 41944 11.34
N2 57387 15.5
H2O 100829 27.2
Ar 699 0.18
Energy Analysis of shift convertor :
Inlet temperature in shift convertor = 356 deg celcius
Outlet Temperature = 426 deg celcius
Using the same thermodynamic approach as above :
Heat released in reaction =- 10.63 MKCal/hr
Sensible heat of reactants and products :
FOR UNREACTED COMPONENTS :
1- CH4 =.033
2- Ar = .01
3- CO = 0.168
4- CO2 = 0.652
5- N2 = 1.245
6- H2O = 2.58
7- H2 = 2.96
Sensible heat of reacting species = 2.52 MKCal/hr
Net sensible heat = 10.46 MKCal/hr
Heat lost in HT Shift Convertor = Heat released Net Sensible heat
Heat Lost = 0.175 MKCal/hr
LT SHIFT CONVERTOR ANALYSIS :
CO Reacted = 6871 NM3/hr
Percentage Conversion = 91.2%
Heat evolved in Reaction = 2.98 MKCal/Hr
Exit Gas Analysis
Component Volumetric flowrate Percentage
CO2 48812 13.19
Steam 93943 25.39
CO 662 369884 0.17
H2 167435 45.26
N2 57393 15.51
CH4 950 0.256
Ar 689 0.186
Energy Analysis :
Heat released in exothermic reaction = 2.98 MKCal/hr
Sensible heats for rise in temperatures =
1- CO=0.0039
2- CH4=0.0086
3- Ar=0.0028
4- H2O=0.651
5- H2=0.941
6- N2=0.33
7- CO2=0.408
Sensible heats of components undergoing reaction = 0.26 MKCal/hr
Net Sensible Heat = 2.605
Net Heat Lost = Net Heat released Net Sensible heat
Net Heat Lost = 0.375 MKCal/hr
Energy Generated by steam for Compressors :
Steam Requirements :
K-421:
HS:
P=38 Kg/cm2
T= 380 C
Flow rate: 61.94 T / hr
H = 3148 KJ/ Kg
Net Energy Generated = 194987120 KJ/hr
K-451 :
HS:
P= 38 kg/cm2
T= 380 C
Flow rate : 15.68 T/hr
H=3148 KJ/hr
Net Energy Generated = 49360649 KJ/hr
05-Section overall balance
Feed Analysis:
Make up Gas :
Flow Rate- 212000 Nm3/hr or 9464.785 Kmol/hr
Composition:
Component Percentage by mole
Methane(CH4) 1.02
N2 26.30
Ar 0.4
H2 72.28
Product Analysis:
Product H2 :
Flow rate : 11508 Nm3/hr or 513 Kmol/hr
Composition:
Component Percentage by mole
Methane (CH4) 0.31
N2 6.33
Ar 0.67
H2 92.69
Purge Gas :
Flow rate : 1700 Nm3/hr or 75.888 Kmol/hr
Composition:
Component Percentage by mole
Methane (CH4) 13.8
N2 22.08
Ar 4.43
H2 52.89
NH3 6.8
Tail Gas :
Flow rate : 6000 Nm3/hr or 267 Kmol/hr
Composition:
Component Percentage by mole
Methane (CH4) 33.61
N2 44.78
Ar 10.08
H2 11.53
NH3 to Urea plant: 79200 Nm3/hr or 3535 Kmol/hr
NH3 to storage : 3640 Nm3/hr or162.4 Kmol/hr
Elemental Carbon Balance :
Inlet :
9464.785 X 0.0102 = 96.535 Kmol/hr
Outlet :
513 X 0.0031 + 75.88 X 0.138 +267 X 0.3361
= 91.329 Kmol/hr
Carbon Loss =Inlet Outlet
=96.535 91.329
=5.206 Kmol/hr or 62.472 Kg/hr
Elemental Hydrogen Balance :
Inlet :
9464.785 X 2 X 0.0102 + 9464.785 X 0.7228
=6937.687 Kmol/hr
Outlet :
513 X 2 X 0.0031 + 0.9269 X 513 + 75.888 X 2 X 0.138 + 75.888 X 1.5 X0.068
+ 267 X 2 X 0.336 + 267 X 0.1153 + 3535 X 1.5 + 162.4 X 1.5
=6235.042 Kmol/hr
Hydrogen Loss = Inlet Outlet
=6937.687 6235.042
=702.63 Kmol/hr or 15738 Nm3/hr or 1405.276 Kg/hr
Latest Technologies for Enhancing the Capacity and Fuel
Consumption of Ammonia Plant
Proposal 1:
KBR Reforming Exchanger System
KRES is a proprietary heat exchanger-based steam reforming technology consisting of a fired
preheater, an autothermal reformer (ATR) and a reforming exchanger. KRES takes the place
of a conventional primary reformer by feeding excess air, natural gas feed and steam to the
ATR and feed and steam in parallel into the upper end of the robust, shell-and-tube reforming
exchanger. The compact ATR and reforming exchanger in combination with the fired
preheater take up much less plot space than a conventional fired steam methane reformer.
The tubes in the KBR reforming exchanger are open-ended and hang from a single tube sheet
at the inlet cold end to minimize expansion problems. They are packed with a conventional
reforming catalyst, which can be easily loaded through a removable top head. The tubes are
accessible and removable as a bundle for maintenance. This simple, proprietary design has
proven to be extremely reliable and maintenance free in commercial operation since 1994.
Heat to drive the reforming reaction is supplied by the effluent gas from the ATR, which
operates in parallel with the reforming exchanger. To ensure adequate heat to drive the
reaction, the ATR receives excess process air, typically 50 percent more than what is required
for nitrogen balance.
The hot ATR effluent enters the lower shell side of the reforming exchanger where it
combines with reformed gas exiting the reforming tubes. This combined gas stream travels
upward through the baffled shell side of the reforming exchanger providing heat needed for
the endothermic reforming reaction
occurring inside the catalyst-filled reforming tubes. In this way, heat energy that would
otherwise be used to generate possibly unneeded steam in a waste heat boiler downstream
of the reformer is used, instead, to replace fuel as the source of heat to drive the reforming
reaction.
Process Flow Diagram of KRES Scheme:
Revamping a plant for capacity increase using conventional technology has
several limitations as the throughputs increase in various sections of the plant.
Examples are:
The size of the reformer furnaces radiant and convection sections needs to
be increased. Further, the capacity of the flue gas side also needs to be
increased.
Pressure drop through the furnace is increased, which reduces the front-end
pressure, including the syngas machine suction pressure. This would
typically reduce plant energy-efficiency and will make revamping of the
syngas machine more expensive.
Heat duty of the reformed gas waste heat boiler increases, making operation
of this critical equipment more severe. Typically, equipment associated
with the steam system waste heat boiler, steam drum, steam superheater,
boiler feed water pumps, piping may all need modification/change which
is expensive.
KRES technology makes revamping of an ammonia plant more economically
attractive by resolving the above issues as follows:
The reforming exchanger adds up to 25% capacity in the reforming section
as additional feed gas and steam mixture is processed in it by recovering the
high-grade waste heat available exit the secondary reformer. Duties on the
furnace services are either maintained or increased only as far as the existing
coils/tubes can take it. As confirmed during the engineering phase of
several revamp projects, the new small mixed-feed coil for the reforming
exchanger is easily accommodated in the existing furnace system.
As the convection duty of the existing furnace is increased relative to its
radiant duty (post revamp compared to the base case), furnace efficiency is
improved in the revamp case.
As the reforming exchanger handles the additional throughput in parallel to
the existing equipment without significantly increasing flows through the
existing key equipment having relatively high pressure drop, the issue of
front-end pressure drop has a resolution.
The reformed gas waste heat boiler now receives a cooler feed gas at 700 to
850C which makes conditions for this critical equipment less severe.
Where applicable, the concern of potential waste heat boiler tube failure can
be addressed by providing such mild conditions, and hence, such a critical
equipment need not be modified or replaced.
As changes in the steam system flow rates can be minimized, replacement
or modification of the high-pressure steam system (e.g. steam drum, waste
heat boiler, steam superheater, BFW pump and piping) can be avoided or
minimized, which contributes to project viability.
Proposal 2:
KBRs Purifier Ammonia Process :
KBRs Purifier Ammonia Process combines the following proprietary technologies to yield an
extremely
reliable, robust, low-energy plant:
Mild reforming with excess air
KBR Purifier
Magnetite ammonia synthesis in a horizontal converter
With KBRs cryogenic Purifier syngas technology, you receive a lower-cost, more robust processing
route to high-purity synthesis gas in ammonia manufacturing plants. The proprietary, front-end
process technology simultaneously removes impurities (i.e., methane, argon) from synthesis gas by
washing it with excess nitrogen while adjusting the hydrogen to nitrogen (H2/N2) ratio to 3:1.
Benefits of Purifier Ammonia Process
Providing a clean, dry, make-up gas to the synthesis loop and simple and precise H2/N2 ratio control,
Purifier technology offers benefits to the entire operation in several key areas:
Low Energy Consumption
A clean, dry make-up gas reduces the load on the synloop compressor and refrigeration systems,
providing operational cost savings
Mild reforming temperatures are used as methane slip is unimportant, which reduces fuel
consumption and increases tube life
Higher loop conversion is achieved with low inerts
Purifier plants operate at the lowest proven energy consumption; a recent plant achieved an energy
consumption of 6.5 Gcal/MT(ISBL, LHV basis)
Purifier Ammonia Pro
Reduced Capital Costs
No separate purge gas recovery unit is needed because purge gas rejected from the synloop is
passed through the Purifier unit
Very clean make-up gas provided by KBRs Purifier lowers synthesis pressure, catalyst volume and
purge rate, which means that smaller synloop equipment can be used
Flexibility
Achieves greater stability and flexibility of operation, since the reforming section does not need to
be tightly controlled to produce a precise H2/N2 ratio
Maintains production even in the event of catalyst deactivation upstream of the Purifier
Reliability
Low reforming temperatures translate to lower stresses in and longer life of reformer tubes
Numerous Purifier plants have run 3 - 4 years without a maintenance sh
PROPOSAL 3:
Objective: To increase the absorption of CO
2
over absorber F-302, thus increasing
the efficiency of absorber and reducing the hydrogen consumption at methanator
R-311.
To achieve the above objective we should replace MEA( Mono
Ethanol Amine) solution with MDEA( Methyl DiEthanol Amine) solution.
Advantages of MDEA Process:
1: MDEA is more efficient carbon dioxide absorber than MEA solution. Results show
that MDEA solution is able to absorb 99.95 % CO
2
compared to 99.58 % CO
2
absorbed by MEA solution. In return less hydrogen gas consumption and less energy
wastage.
2: Low inerts make-up in synthesis gas due to low CO2 slip. Low CO2 slip with
product gas has further advantages such as less consumption of H2 in methanator,
higher conversion per pass in synthesis converter due to less inerts and reduction in
purge gas from synthesis loop.
3: Utilisation of all the existing equipments i.e. not making any changes in the
system.
4: Lower MDEA make up requirement.
5: MDEA (Methyl diethanol amine) is environment friendly and biodegradable
chemical. MEA solution is a corrosive solution, while MDEA is non-corrosive.
Hence MDEA system does not require any corrosion inhibitor as compared to MEA
solution which uses V
2
O
5
which is carcinogenic in nature.
PROPOSAL 4:
Objective: To reduce the energy consumption in Carbon Dioxide removal section
and make the process more energy efficient.
Existing CO
2
removal section
Modified CO
2
removal section
If the process stream from the top of F-303 is again diverted to F-301 regenerator,
and the residue of B-301 is brought back to the absorber. This modification done
with MDEA solution reduces the energy requirements of the plant by 50 60% of
the current energy consumption.
PROFIT:
By using the above combination of MDEA solution and Two stage removal process
we can optimize the plant for more production. As MDEA solution absorbs 0.37%
more than the existing MEA and GV solution, and preventing the use carcinogenic
corrosion inhibitor V
2
O
5
, therefore cost effective.
Second, by using the Two stage removal process with MDEA solution the removal
process will be optimized for less energy consumption, thus less energy and more
cost effective.
Following proposals are based on KAAP (Kelloggs
Advanced Ammonia Process) Technology based on
some advancement over traditional ammonia process
technology :
Proposal 5:
Gas Heated Reformers
This technologies includes the use of Gas Heated Reformers (GHR), which are
tubular gas-gas exchangers. In the GHR, the secondary reformer outlet gases
supply the reforming heat. Though it is not presently being used widely, GHR
has certain advantages over fired furnaces. Table 1 shows a list of these
advantages. Although GHR results in reduced energy consumption, a
comprehensive energy conservation network should be established to maximize
the benefits of a GHR system.
Table 1: Advantages of Gas Heated Reformers
Fired Furnace Gas Heated Reformers
Large volumes Smaller volumes
Larger surface area and heat loss Reduced surface area and heat loss
Complex instrumentation Simplified instrumentation
High maintenance costs Low maintenance costs
Large convection zone No convection zone
Stack losses No stack losses
High fixed capital costs Low fixed capital costs
Reduced catalyst tube loss from
high temperature and uneven heat
distribution
Longer tube life due to uniform
heat distribution
Increased downtime required for
shut down
Reduced downtime required for
shut down
Well established process Yet to gain wide acceptance
Proposal 6:
Hydrogen Separation
Lechatelier's Principle states that a reaction equilibrium can be shifted
by applying external forces. This offers a means of removing products
from the reaction mixture to increase the conversion per pass. In
reforming, experiments have been performed up to 500
0
C (932
0
F)
and 20 bar (294 psig) using a palladium membrane to remove the
product hydrogen. These experiments have results in a significant
increase in methane conversion as can be seen by the following case
study.
Case Study on the Membrane Separation Process
The separation of hydrogen from the product gas of
the reforming process can result in significant productivity
gains when compared to the current processes being
employed. The base case for this study is a conventional
steam reforming plant based on natural gas operating at
1750 tonnes per day. The operating conditions of the
plant are assumed to be the same as those typically
employed today and the only modification is the
introduction of hydrogen separation. The tests for the
membrane separation have been carried out at 500
0
C
(932
0
F) and 20 bar (294 psig), these conditions will
function as upper limits for the process to be considered
in this study. Membrane units will be considered after
the primary reformer (at 60% hydrogen separation), after
the secondary reformer (at 60% hydrogen separation),
and after the High Temperature Shift (HTS) converters (at
a 50% hydrogen separation)
The following assumptions are made in this case study:
1. The natural gas feed at the primary reformer is the
same for both cases.
2. The primary reformer exit temperature is the same
for both units.
3. The primary reformer operating pressure is the
same for both units.
4. The process air is fed to the secondary reformer at
optimal conditions and any remaining nitrogen that
is required is supplied through an Air Separation
Unit (ASU) and is available at 0.1 kg/cm
2
(1.42 psig)
5. Any extra energy consumption in the ASU is
considered for the revamp case.
6. All of the heat from the process gas from the
primary reformer to the carbon dioxide removal
section is used in a steam network.
7. No changes in the carbon dioxide removal system
are considered.
8. The pressure drop across the front end of the
process is kept constant for both systems, thus the
synthesis gas compressor suction pressure remains
constant.
9. The loop pressure is the same for both processes
and is controlled by changing the purge gas quantity.
10. The existing compressors are capable of
handling any additional loads.
11. No scheme changes are considered in the
synthesis loop.
12. All hydrogen from the membrane separation
unit is available at 9.0 kg/cm
2
(128 psig)
13. The productivity analysis is carried out on the
ammonia plant only (the urea plant is excluded)
14. A complete steam balance is included on both
processes. Changes in the steam balance are
considered for:
Steam generation from the front end of the
processes
Steam generation from the back end of the
processes
Additional steam in the carbon dioxide removal
section caused by a reduction in the heat available
from the process gas
Additional power for the synthesis compressor due
to changes in flow and composition
Additional power in the ammonia refrigeration
compressor
Reduced load on the process air compressor
Additional power for low pressure hydrogen
separated through membranes
Additional power for nitrogen compression
Additional power for the air compressors of the ASU
Small changes in other drives and small equipment
Comparison Between Conventional Reforming and
Reforming with Hydrogen Separation
Production rise from 1750
to 1854 tonnes per day
+6.0% rise in capacity
Process Change Energy Change (Gcal/tonne)
Gain in feed and fuel
including steam
superheater
+0.36
Loss in steam generation
(front end)
0.00
Loss in steam generation
(back end)
-0.02
Loss in additional steam for
carbon dioxide removal
-0.27
Gain in energy in synthesis +0.01
gas compressor
Extra energy in refrigeration
compressor
0.00
Gain in energy in process air
compressor
+0.16
Extra power in hydrogen
compressor
-0.22
Extra power for nitrogen
from ASU
-0.12
Steam savings in primary
reformer
+0.08
Other rotary drives and
equipment
+0.04
Total Gain +0.02
It is evident from these results that the major losses occur
in the carbon dioxide removal section of the plant. These
losses are the result of consuming additional steam and
compression energy for hydrogen separation. With
additional minimization of these losses, additional savings
can result. For a production gain of 6% over the base
case, the energy saving is 0.02 Gcal/tonne (0.08
MBtu/tonne).
This development could yield savings by increasing methane
conversion in reformers and increasing the carbon monoxide
conversion in shift reactors. The energy savings can be as high as 0.50
Gcal/tonne (1.98 MBtu/tonne) depending on the adopted process
configuration. Hydrogen separation technology can also result in
increased ammonia plant capacity as illustrated in the above case
study.
The reduced air requirement (about 80% of conventional plants) in
the secondary reformer is required with a 60% hydrogen removal rate
in the reformer. This will also require an additional source of
nitrogen. Therefore, the technologies in which nitrogen is being
added separately, either from an Air Separation Unit (ASU) or from
any other sources, will become more important in this case.
Proposal 7:
Synthesis Catalyst
After almost 90 years of a monopoly in the ammonia synthesis market, iron
catalyst has not been replaced by a precious metal (ruthenium) based catalyst
used in the KAAP developed by Kellogg. The KAAP catalyst is reported to be
40% more active than iron catalysts.
Research work on low temperature and low pressure catalysts to produce
ammonia at 20-40 kg/cm
2
g and 100
0
C is being performed at Project and
Development India Ltd. (PDIL) according to their in-house magazine. The
catalyst is based on cobalt and ruthenium metals and has exhibited few
encouraging results.