2500 MTPD of Ammonia From Naphtha: Nfc-Iet Multan
2500 MTPD of Ammonia From Naphtha: Nfc-Iet Multan
2500 MTPD of Ammonia From Naphtha: Nfc-Iet Multan
Contents
INTRODUCTION:..........................................................................................................................
1.1 Ammonia...............................................................................................................................
1.1.1 History of Ammonia...........................................................................................................
1.1.3 Raw Material Used.............................................................................................................
1.1.4 Anhydrous Ammonia Properties:.......................................................................................
1.1.5 Expansion in the industry...................................................................................................
1.1.5.1 Improvement in NH3 Production process:.....................................................................
1.1.6 Uses of Ammonia:............................................................................................................
1.1.6.1 Minor and Emerging Uses:............................................................................................
1.2 Naphtha................................................................................................................................
1.2.1 Properties:.........................................................................................................................
1.2.2 Production of Naphtha in Refineries and Uses:................................................................
1.2.3 Exported Naphtha specification of ARL:.........................................................................
1.3 Ammonia in Pakistan:..........................................................................................................
1.3.1 PakArab fertilizer ltd. (Pfl) Multan..................................................................................
1.3.2 Fauji fertilizer ltd. Goth Macchi.......................................................................................
1.3.2.1 Base Unit-Goth Machhi(Plant-1)...............................................................................
1.3.2.2 Expansion Unit-Goth Machhi(Plant-II).....................................................................
1.3.3 FFC Ltd. Mirpur Mathelo.:...............................................................................................
1.3.4 Agritech Ltd. Daudkhel:...................................................................................................
1.3.5 Engro Chemicals ltd. Dharki:...........................................................................................
1.3.6 Dawood Hercules Chemicals Limited:.............................................................................
1.4 Ammonia Production in Pakistan:.......................................................................................
1.5 Naphtha Exports at Loss:.....................................................................................................
1.6 Capacity:..............................................................................................................................
MANUFACTURING PROCESS..................................................................................................
2.1 Haldor Topsoe A/S Process.................................................................................................
2.2 Kellogg Brown and Roots Advanced Ammonia Process (KAAP).....................................
2.3 Krupp Uhde GmbH ammonia Process................................................................................
2.4 Haber process:.....................................................................................................................
2.5 Braun Purifier process:........................................................................................................
2.6 Foster Wheeler Process:......................................................................................................
REFERENCES............................................................................................................................
CHAPTER 1
INTRODUCTION
INTRODUCTION:
In this chapter we have discussed about Ammonia and Naphtha. The
whole chapter comprises of their history, physical and chemical properties, Raw
materials used for their manufacturing, Expansion in overall industries in Pakistan
according to the production point of view and about the market analysis and survey.
1.1 Ammonia
Ammonia is an intermediate product in the manufacture of nitrogenous fertilizers. It is
also used for direct application to the soil and in aqua condition with solutions of other
nitrogenous fertilizers like ammonium nitrate and/or urea. Besides these, ammonia finds
applications in the production of nitric acid, soda ash, cleaning agents, leather tanning,
petroleum refining, pulp & paper industry, textiles, refrigeration, rubber & synthetic resin
industries, explosives and food & beverages.
The process became commercial Haber-Bosch process. Although several processes have
developed since 1913.The main differences were the methods for the preparation of
synthesis gas, the purification of synthesis gas, the design of ammonia convertor and
method of receiving ammonia from converted flue gas.
Prior to 1945, coat and coke oven gas was the major raw material used for the production
of hydrogen required for ammonia synthesis. During the past 35 years, there has been a
trend towards the use of petroleum products. Most of the plants built during the past 25
years, throughout the world designed for the use of a natural gas, heavy oil as feed
material. During last 15 years, Naphtha has become the most popular feed material in the
areas where natural gas is not present. At present almost all of the ammonia plants in
USA are based on natural gas.
Ammonia is produced by the reaction between nitrogen (N2) and hydrogen (H2)
N2 + 3H2 → 2NH3
Source of Nitrogen is atmospheric air and following hydrocarbons are generally used as
the source of hydrogen.
Natural gas
Naphtha
Heavy Oil
Other sources of hydrogen which were used earlier for manufacture of Ammonia are:
1) Semi-water gas made by gasification of coke/ coal with steam.
2) Hydrogen produced by electrolysis of water.
3) By product Hydrogen from chlorine production.
Chemical Properties:
Major expansion of the ammonia industry began in 1963.The demand for nitrogen based
fertilizer throughout the world and the prospects for increased consumption in future
years stimulate fertilizer producers to build many new ammonia plants. During the last 8
years, a trend has developed towards building large scale train plants with capacities of
600 to 1500 tons per day. During the last quarter century many improvements have been
made in plant equipment, catalysts and instrumentation. These developments have
contributed to substantiate reduction in the capital cost and operation costs of ammonia
plants.
In 1960, the world production of ammonia was about 13 million ton. The use of ammonia
can be apprehended by the fact that in 1967, 12 million of ammonia was manufactured in
United States of America raised to 18 million tons the very next year.
Major development of ammonia began in 1963, so that ammonia requirement for the
fertilizer industry can be fulfilled. During the last quarter century many improvements
have been made in plant design technology. Significant improvements have been made
in plant equipment catalyst and instrumentation .These developments have caused a
substantiate reduction in capital cost and operation costs of ammonia plants. Research
work is not so ancient .At the time of Independence, there was no ammonia industry in
Pakistan. The trend of ammonia industry was developed with the use of fertilizer. The
start of fertilizer/ammonia industry was taken up in after 1960’s during the rule of Field
Marshal Ayyub Khan. Afterwards many fertilizer industries were set up in Pakistan in
private as well as public sector. Now National Fertilizer Corporation of Pakistan is
making its best efforts for the prosperity.
Since 1954the following sweeping changing in the technology of ammonia manufacture
has taken place.
1 Feed ranging from natural gas to naphtha have been processed by steam
hydrocarbon reforming at pressure up to 500lb/in2 gauge.
2 Electric power consumption has been reduced to practically zero due primarily
to the use of a highly efficient energy cycle which incorporates high pressure
steam generation in conjunction with the maximum use of turbine drives to
pumps and centrifugal compressors.
3 Enormous improvements in the gas purification processes .several low utility
process are available for CO2 removal including promoted MEA, promoted hot
potassium carbonate process, sulfinol, the two stage Tri ethanol amine /Mon
ethanolamine system and others. Moreover, removal of residual CO has been
enormously simplified by the use of the methanation system. Space
requirements for the purification system have been minimized.
4 Improved heat recovery, particularly in the reformer effluent system and the
various catalyst reaction services.
5 Efficient use for steam
6 Use of higher activity catalyst for all the process services. The introduction of
low temperature shift conversion catalyst has simplified the design of the raw
gas generation system and permitted substantial reduction in the quantity of feed
processed in the reformer because of the associated reduction in purge in the
synthesis loop.
7 Plant capacities have been increased from 600 to 1700 tons/day as 100% single
train operations throughout the unit including the ammonia convertor. In
addition, there have been significant improvements in the fabrication of
ammonia convertors. Full closure convertors can be offered in a wide range of
capacities and operating pressures. Moreover, the internal layout of ammonia
convertors have been modified in the direction of low pressure drop which still
retaining efficient distribution of gas through the catalyst beds. The number of
catalyst beds for the quench –type convertor has been optimized. Also, more use
has been made of reduced size synthesis catalyst which has reduced both the
volume of catalyst and the convertor size by 10-25% depending on the size of
catalyst used and the available pressure drop of the loop.
8 Improvement in compressor design for all process service. Centrifugal
compressors can be provided for the synthesis gas service for pressure up to
4700lb/in(g) for size in excess of 1700 tons /day operating over a wide range of
speeds and horsepower.
9 Development of improved method for feed desulfurization including hydro
desulphurization of naphtha feeds. Improvements in both cobalt molybdenum
catalyst and zinc oxide sulfur absorbent catalyst have enabled all feeds to be
desulfurized to levels of less than 0.25 ppm sulfur, thus ensuring protection of
reforming catalyst against sulfur poisons with a resultant long catalyst life.
1940 to 1952
Main features:
Capacity : 150T/D
CO2 Removal system : Water wash, 20% MEA
No. of NH3 converter : 3
Process characteristics
1 .Low pressure catalyst reforming of natural gas i.e. (0.6-1.0)kg/cm2
2. Low pressure efficiency High power consumption.
1953
Main features:
Capacity : 160T/D
CO2 Removal system : 20% MEA
No. of NH3 converter : 2
Process characteristics
1. First increase in reforming i.e. 4.2 kg/cm2
2. Substantial reduction in power consumption
3. Gas holder and associated operation eliminated
1955
Main features:
Capacity : 300T/D
CO2 Removal system : 20% MEA Hot k2co3
Process characteristics
1. Reduction in Fuel & power consumption
2. First use of centrifugal compression in raw synthesis gas service.
3. Additional feeds processed include refinery gas and naphtha.
4. Use of Hot K2CO3 for CO2 removal.
5. Further increase in reformer pressure i.e. 8.8 kg/cm2
1960 to 1962
Main features:
Capacity : 360T/D
CO2 Removal system : 20% MEA
No. of NH3 converter : 1
Process characteristics
1. Further increase in reformer pressure i.e. (14.5-18.4)kg/cm2
2. Elimination of copper liquor system.
3. Elimination of compression in raw gas.
4. Use of high air pre-heat for secondary reformer.
5. Internal main folding of reformer catalyst lube to reduce heat losses.
6. Greater recovery of heat of reaction for all catalytic services.
1963
Main features:
Capacity : 320T/D
CO2 Removal system : 20% MEA
No. of NH3 converter : 1
Process characteristics
Further increase in reformer pressure i.e. (21-28.3)kg/cm2
High thermal efficiency, reduced fuel consumption
Introduction of improved low temperature co shift catalyst.
Reduced purge rate in synthesis loop.
1964
Main features:
Capacity : 600T/D
CO2 Removal system : 20% MEA
No. of NH3 converter : 1
Process characteristics
1. First single train 600 ton ammonia plant.
2. First use of centrifugal compressor to compress synthesis gas to 150 atm.
3. Approximately 80% of all compression horsepower (including air +
Refrigeration) based on use of centrifugal machines.
1965 to 1972
Main features:
TEA/MEA
No. of NH3 converter : 1
Process characteristics
1. Further increase in reformer pressure in conjunction with low pressure
synthesis i.e. (31.7-33.5)kg/cm2.
2. Entire synthesis gas compression (including recycling service) handled by a
two stage centrifugal compressor for synthesis pressure up to 220 atm.
Fertilizer
Approximately 83% (as of 2004) of ammonia is used as fertilizers either as its salts or as
solutions. Consuming more than 1% of all man-made power, the production of ammonia
is a significant component of the world energy budget.
Cleaner
Household ammonia is a solution of NH 3 in water (i.e., ammonium hydroxide) used as a
general purpose cleaner for many surfaces. Because ammonia results in a relatively
streak-free shine, one of its most common uses is to clean glass, porcelain and stainless
steel. It is also frequently used for cleaning ovens and soaking items to loosen baked-on
grime. Household ammonia ranges in concentration from 5 to 10 weight percent
ammonia.
Refrigeration – R717
Because of its favorable vaporization properties, ammonia is an attractive refrigerant. It
was commonly used prior to the popularization of chlorofluorocarbons (Freon’s).
Anhydrous ammonia is widely used in industrial refrigeration applications and hockey
rinks because of its high energy and low cost. The Kalina cycle, which is of growing
importance to geothermal power plants, depends on the wide boiling range of the
ammonia-water mixture. Ammonia is used less frequently in commercial applications,
such as in grocery store freezer cases and refrigerated displays due to its toxicity.
As a fuel
Ammonia was used during World War II to power buses in Belgium, and in engine and
solar energy applications prior to 1900. Liquid ammonia was used as the fuel of the
rocket airplane, the X-15. Although not as powerful as other fuels, it left no soot in the
reusable rocket engine and its density approximately matches the density of the oxidizer,
liquid oxygen, which simplified the aircraft's design.
As a stimulant in sports
Ammonia has found significant use in various sports – particularly the strength sports
of power lifting and Olympic weightlifting as a respiratory stimulant (psychoactive
drugs).
Textile
Liquid ammonia is used for treatment of cotton materials, give properties
like Mercerization (It is a treatment for cotton fabric and thread that gives fabric or yarns
a lustrous appearance and strengthens them using alkalies). In particular, it is used for
pre-washing of wool.
Lifting gas
At standard temperature and pressure ammonia is lighter than air, and has approximately
60% of the lifting power of hydrogen or helium. Ammonia has sometimes been used to
fill weather balloons as a lifting gas. Because of its relatively high boiling point
(compared to helium and hydrogen), ammonia could potentially be refrigerated and
liquefied aboard an airship to reduce lift and add ballast (and returned to a gas to add lift
and reduce ballast).
Woodworking
Ammonia was historically used to darken quarter sawn white oak in Arts & Crafts and
Mission style furniture. Ammonia fumes react with the natural tannins in the wood and
cause it to change colors.
1.2 Naphtha
Naphtha is used primarily as feedstock for producing high octanegasoline (via the
catalytic reforming process). It is also used in the bitumen mining industry as a diluents,
the petrochemical industry for producing olefins in steam crackers, and the chemical
industry for solvent (cleaning) applications. Common products made with it include
lighter fluid, fuel for camp stoves, and some cleaning solvents.
1.2.1 Properties:
To obtain the product known as naphtha, a complex soup of chemicals is broken into
another range of chemicals, which are then graded and isolated mainly by their specific
gravity and volatility.
Naphtha is insoluble in water.
They are colorless (with a kerosene odor) or red-brown (with an aromatic odor).
They are incompatible with strong oxidizers. Less dense naphtha’s ("light
naphtha’s") have higher paraffin content. They are therefore also
called paraffinic naphtha. The denser naphtha’s ("heavy naphtha’s") are usually
richer in naphthenes and aromatics.
Heavynaphtha
The "heavy" naphtha can also be used in the petrochemical industry, but they are more
often used as feedstock for refinery catalytic reformers where they convert the lower
octane naphtha to a higher octane product called reformate. Alternative names for these
types are "straight run benzene" (SRB) or "heavy virgin naphtha" (HVN).
Additional applications
Naphtha’s are also used in other applications, such as:
at 50°C (122°F)
Mercaptan Sulphur ppm D-3227 3
Min
Total Sulphur ppm D-1266 50
Max
Reid Vapor Pressure psi D-323 12
Max
@ 37.8 kpa
Lead ppb IP-224 25
Max
Distillation o
C ASTM-86
IBP 25
Min
nutrient mining. And there is insufficient and inadequate use of fertilizer. The industries
that produce ammonia in Pakistan are listed below:
1. PakArab fertilizer ltd. Multan
2. Fauji fertilizer ltd. Goth Macchi.
3. Paksaudi Fertilizers (Now FFC) Ltd. Mirpur Mathelo.
4. Pak American (Agritech) Ltd. Daudkhel
5. Engro Chemicals ltd. Dharki.
6. Dawood Hercules Ltd. Lahore.
Exports of naphtha from Pakistan also dropped in recent months. The data shows that the
cumulative quantity of two different grades of the hydrocarbon mixture exported from the
country in the first eight months of the current fiscal stood at 895,588 tons, compared
with almost 920,000 tons exported in the corresponding period of last year. Overall
production of local refineries has been limited in the past few months.
Naphtha is a by-product of crude oil, obtained through refineries. The substance is used
for making paraxylene, which is in turn used to make polyester fibre utilized by the
textile sector.
Our refineries cannot control the proportion of different petroleum products made in the
refining process, so even though there is no capacity to make paraxylene in the country,
we cannot reduce the production of naphtha for other variants.
The analyst explained that naphtha is exported at relatively cheaper rates, only to be
imported in the form of paraxylene which is a lot more costly.
While the quantity of naphtha exports has not registered a significant increase, rising
prices helped shore up the export value. During the July-February period of year 2011
$698.7 million worth of naphtha was exported, compared with exports of $609.8 million
during the same period last year. Asian naphtha prices climbed above $1000 per ton in
March for the first time in 30 months in 2011.different refineries that export naphtha on
yearly bases are listed under.
REFINERYEXPORT (Tons/Annum)
NRL 300,000
PRL 178460
ARL 200,000
BOSICOR 37,000
Dhodak 83,000
PARCO---
Total Country Exports Potential 798460
1.6Capacity:
Pakistan is likely to face shortage of up to 400,000 tons urea in December, 2011 due to
unavailability of natural gas used as a raw material for ammonia that further produces
urea. Even after imports by the Trading Corporation of Pakistan (TCP) of 440,000 tons.
There would be a urea shortage of at least 200,000 tons in December 2011, which is the
peak urea consumption time in Rabi because of wheat sowing. It can go up to 400,000
tons in case of delay in import. Majority of urea shipments are coming from Russia and
China, which might arrive at Gwadar port in 20 to 25 days.
Industry sources said production losses due to continued curtailment of gas from the Sui
Northern Gas Pipelines Limited (SNGPL) to urea manufacturers are also complicating
this situation. Rabi Season could still be shielded from acute shortage if all fertilizer
plants were operated in November and December to cover December demand of up to
800,000 tons to 850,000 tons of urea. In order to overcome the shortage of natural gas
which is a raw material for ammonia that is used in urea manufacturing. We have decided
to build a plant that can produce 2500 MTPD of ammonia using naphtha as a source
instead of natural gas. It may provide benefit in economics of country. And we may
reduce the short fall.
CHAPTER 2
PROCESS DESCRIPTION
MANUFACTURING PROCESS
The synthesis gas for manufacture of Ammonia is produced by steam reformingor partial
oxidation of Hydrocarbon feed. In most industries steam reforming isused normally.The
various processes used commercially in industries for production of Ammonia are
The company’s low energy ammonia process uses the conventional sequence of process
steps which are optimized by the introduction of improved catalysts, new equipment
design and extensive process optimization studies. A pre-reformer containing nickel
catalyst has been also provided upstream of primary reformer for converting all the
higher hydrocarbons, so that only methane, carbon monoxide, carbon dioxide, hydrogen
and steam are present in the product gas. Firing in primary reformer is reduced by 15%
due to pre-reformer. Highly active shift catalyst ensures the lowest carbon monoxide (less
incomplete combustion) at the exit of converters and thus highest utilization of feedstock.
New temperature resistant iron free catalyst makes it possible to operate at low steam to
carbon ratio at high temperature shift converter. The company has also developed Heat
Exchange Reforming Process. Low energy CO2 removal processes, such as selexol,
MDEA or low heat potassium carbonate, are used. Topsoe has developed new converters
especially for high conversion loops.
KAAP uses a high-pressure heat exchange based steam reforming process integrated with
a low-pressure advanced ammonia synthesis process. Raw synthesis gas is produced by
steam reforming of hydrocarbon in a heat exchange based system under pressure, based
on Kellogg Brown and Root Reforming Exchange System (KRES). KRES also reduces
energy consumption and capital cost besides reduced emission and enhanced reliability.
The Krupp Uhde Gmbh process uses conventional steam reforming for synthesis gas
generation (front end) and a medium-pressure ammonia synthesis loop. The primary
reforming is carried out at pressure 40 bar and temperature range of 800-8500C. The
steam reformer is top fired and tubes are made of centrifugal high alloy steel which
enhances reliability. Process air is added in secondary reformer through nozzles installed
in the wall of vessel. This provides proper mixing of the air and reformer gas. Subsequent
high pressure steam generation & superheating, guarantee maximum heat usage to
achieve energy efficiency. Carbon monoxide is converted to carbon dioxide in HT and
LT shift converters. The MDEA or Benfield system is used for carbon dioxide removal.
The ammonia synthesis loop uses two ammonia converters with three catalyst beds with
waste heat boiler located downstream of each reactor. The converters have small grain
iron catalyst. The radial flow concept minimizes pressure drop and allows maximum
ammonia conversion.
In the secondary reformer 1.5 times the stoichiometric quantity of air is used. This
increases the heat load and reduces the radiant duty of the primary reformer to less than
two thirds its usual duty. Excess nitrogen is removed by a cryogenic purification unit
after methanation occurs.
Large air compressors used are driven by gas turbines. Owing to the high purity of
synthesis gases, lower recylce gas flow, lower refrigeration duty and lower purge duty
will suffice.
In the secondary reformer excess air is used as in the previous case. Instead of treating
the whole feed in primary reformer, some bypass is fed to the secondary reformer. Partial
reaction in primary reformer will allow for a lower steam to carbon ratio. Excess air used
is much higher than in the case of Braun purifier process. A cryogenic unit removes
nitrogen form the exit gases leaving the methanator. CO 2 is removed using physical
solvents. Absorption system provides refrigeration for ammonia recovery.
For the production of ammonia we have decided to select the Haldor topsoe because of
its energy efficient nature. Ammonia production usually requires the formation of
molecular hydrogen followed by contacting the hydrogen with molecular nitrogen over a
catalyst for ammonia synthesis.Topsoe's low energy ammonia process scheme can be
optimized for a wide range of operating conditions by selecting proper process
technology and by adjusting the process parameters. Topsoe's ammonia plant designs are
characterised by being highly energy efficient.
efficiency and conversion of complete process and the large and massive compressors
which are used in Claude process are required to maintaining 900 atm which
cost millions of Dollars are avoided in Haldor Topsoe and is thus more economic and
good especially for large capacity process. Also the life of the converter is very long and
ammonia is removed by water-cooling and by knockout drum.Through this method we
can achieve 15.8 mol% of ammonia per pass.
2.8.1 Advantages:
2.8.2 Disadvantages:
2.9.2 Desulfurizer
As the virgin naphtha had high sulphur content, the Hydrofining or Desulphurization
process is used to bring down the sulphur content to 2 ppm by a suitable process in which
the preheated mixture of vaporized naphtha and hydrogen rich washed purge gas is
superheated and routed to the reactor where it flows over Cobalt Molybdenum catalyst at
a temperature of about 673 K or 399 oC.
H2 + S H2S
H2S + ZnO H2 O +ZnS
The sulfur content is reduced to less than 5ppm. The mixture is sent to Final
Desulphurizer where the last traces of organic sulphur is converted to H 2S by reaction
over COMoX catalyst and H2S is removed by an Absorbing Column containing ZnO.
Subsequently Naphtha vapors are mixed with steam and sent to reforming section.
Pre-Reforming
Adiabatic prereforming can be used for steam reforming of feed stock ranging from
natural gas to heavy naphtha. In this all higher hydrocarbons are converted into a mixture
of carbon oxides, hydrogen and methane. When it is installed, the primary reformer has
to reform methane only, and at the same time at sulphur free conditions, because
prereforming catalyst will pick up sulphur components quantitatively. This is one of the
reasons for allowing much higher heat flux in the high flux reformer.
The prereformer feed can be reheated to 650 oC before
entering the primary reformer. This will result in reduced firing in the primary reformer,
and thereby reduced fuel consumption. When the hot flue gas is used to reheat the
reformer feed, the amount of heat available for HP steam production is reduced. This
would result in a reduced HP steam production in the ammonia plant.
Primary Reformer
In the first stage desulfurized naphtha is mixed with steam in a tubular reforming furnace.
The reformation reactions occur at a temperature of about 673K. Steam to carbon ration
must be maintained between 3.5 and 4.5 to ensure that Carbon deposition does not occur.
CnHm + nH2O nCO + (n+m/2) H2
CO + H2O CO2 + H2
CO + 3H2 CH4 + H2O
The overall reaction is highly exothermic and the outlet temperature is about1093 K. The
primary reforming process is characterized by a low pressure.
Secondary Reformer
The gases from the primary reformer are mixed with air and steam at the outlet
temperature of the primary reformer. The remaining hydrocarbon like methane is further
subjected to reformation and the overall yield of hydrogen is increased. Air is mixed to
form a mixture of H2 and N2 for the synthesis process.
CH4 + H2O CO +3 H2
Initially the carbon monoxide burns in air to produce carbon dioxide and the temperature
increases to about 1200 oC. Then adiabatic reaction of methane with steam occurs and the
outlet temperature decreases to about 1000 oC at the outlet.
2.9.4.1 HTSC
2.9.4.2 LTSC
The reaction occurs at a temperature of about 523 K. Concentration of CO in the exit gas
is reduced to about 0.3 % by volume. The gas leaving the HT converter is then cooled
and sent to LT converter where the gas passes over Copper catalyst. The remaining CO is
converted to CO2 in shift convertor.
2.9.6 Methanation
Even trace quantities of Carbon monoxide and Carbon dioxide will act as catalyst poisons
in the synthesis loop. Hence they must be removed by conversion into methane. Methane
though not an inert gas is nevertheless inert in the ammonia synthesis process. The
reaction in the methanator occurs at a temperature of about 573 to 673 K. The exit gases
contain steam are condensed and cooled before being stored for the synthesis loop.
Synthesis gas is compressed to about 50 MPa and heated t about 673 K before passing
through the catalyst beds. The reaction being a reversible one high pressure favors the
forward phase. As the concentration of ammonia in the exit gas is low, recycling of gas is
necessary. The converter used is a vertical type of converter. Catalyst activity increases
with increase in temperature; hence ideal temperature profile is one in which rate of
ammonia production is a maximum at all parts of the bed. In the upper part of the
converter the concentration of ammonia being low the temperature is high ensuring high
reaction rates. In the lower parts temperature must be low due to increasing influence of
equilibrium concentration.
CHAPTER 3
MATERIAL BALANCE
MATERIAL BALANCE
3.1 Primary Reformer:
Primary Reformer
Conversion =90%
C8H18 = 680,000 tons/yr C8H18 = 7762.56
kg/hr
C8H18 = 77625.57 kg/hr H2 = x
CO = y
CO2 = z
Reactions:
C8H18 + 8 H2 O 8 CO + 17 H2
CO + H2 O CO2 + H2
Basis:
Degree Of Freedom:
Unknown Equations
X C
Y H
Z O
Steam Balance:
Carbon Balance:
Hydrogen Balance:
Oxygen Balance:
INPUT OUTPUT
C8H18 = 77625.57 kg/hr C8H18 = 7762.56 kg/hr
Steam = 110310 kg/hr H2 = 24513.34 kg/hr
CO = 133446 kg/hr
CO2 = 8179.68 kg/hr
Secondary Reformer
Conversion = 99%
Basis:
Naphtha = 7762.56 kg/hr
Reaction:
C8H18 + 12.5 O2 + N2 8 CO2 + H2 O + N2
Degree of Freedom:
Unknown Equations
X C
Y H
Z O
Air Balance:
Carbon Balance:
Hydrogen Balance:
Oxygen Balance:
N2 Balance:
INPUT OUTPUT
C8H18 = 7762.56 kg/hr C8H18 = 77.62 kg/hr
Air = 27246.55 kg/hr CO2 = 23792.4 kg/hr
H2O (v) = 10931.6 kg/hr
O2 = 9942.98 kg/hr
N2 = 91216.7 kg/hr
HTSC
Conversion = 70%
CO = 133446 kg/hr CO = 40034
kg/hr
CO2 = x
H2 = y
H2 O (v) = z
Basis:
Carbon Monoxide = 133446 kg/hr
Reaction:
CO + H2O (v) CO2 + H2
Degree of Freedom:
Unknown Equations
X C
Y H
Z O
Steam Balance:
Carbon Balance:
Hydrogen Balance:
Oxygen Balance:
INPUT OUTPUT
CO = 133446 kg/hr CO = 40034 kg/hr
Steam = 85786.7 kg/hr CO2 = 147182.76 kg/hr
H2 = 6774.6 kg/hr
LTSC
Conversion = 99%
CO = 40034 kg/hr CO = 40034
kg/hr
CO2 = x
H2 = y
H2 O (v) = z
Basis:
Carbon monoxide = 40034 kg/hr
Reaction:
CO + H2 O (v) CO2 + H2
Degree of Freedom:
Unknown Equations
X C
Y H
Z O
Steam Balance:
Carbon Balance:
Hydrogen Balance:
Oxygen Balance:
Z = 122.35 kg/hr
INPUT OUTPUT
CO = 40034 kg/hr CO = 400.34 kg/hr
Steam = 25736.14 kg/hr CO2 = 62448 kg/hr
H2 = 2846.1 kg/hr
H2O (v) = 122.35 kg/hr
Total Components:
CO2 = (8179.68 + 23792.4 + 147182.76 + 62448) kg/hr
CO2 = 241602.84 kg/hr
CO =400.34 kg/hr
H2 = (24513.34 + 6774.6 + 2846.1) kg/hr
H2 = 34134.04 kg/hr
N2 = 91216.7 kg/hr
3.5 Absorber:
The absorber is used to absorb Carbon Dioxide from mixture of gases. Here
we are using Benfield solution for the absorption of CO2.
Absorber
Absorption = 99.9%
Reaction:
INPUT OUTPUT
CO2 = 241602 kg/hr CO2 = 241.60 kg/hr
K2CO3. H2O = 296512.58 kg/hr
3.6 Methanator:
H2 = 34134.04 kg/hr
Reactions:
Degree of Freedom:
Unknown Equations
X C
Y H
Z O
Carbon Balance:
Hydrogen Balance:
Oxygen Balance:
INPUT OUTPUT
CO2 = 241.60 kg/hr CH4 = 313.45 kg/hr
CO = 400.34 kg/hr H2O (v) = 455.03 kg/hr
H2 = 34134.04 kg/hr H2 = 34005.54 kg/hr
CO = 4 kg/hr
CO2 = 2.42 kg/hr
3.7 Concertor:
N2 = 91216.7kg/hr
Convertor
Conversion = 98%
NH3 = x
H2 = 19546.44kg/hr N2 = 1824.33
kg/hr
H2 = 390.93
kg/hr
Reaction:
N2 + 3 H2 2 NH3
Hydrogen Calculations:
Nitrogen Balance:
INPUT OUTPUT
N2 = 91216.7kg/hr NH3 = 110834.4kg/hr
H2 = 19546.44kg/hr N2 = 1824.33kg/hr
H2 = 390.93kg/hr
Total Ammonia:
Ammonia = 110834.4(kg/hr) x (24 hr /1day) x (1 MT /1000 kg)
Ammonia = 2660 MTPD
This is quite near to our decided capacity that is 2500 MTPD.
CHAPTER 4
ENERGY BALANCE
ENERGY BALANCE
4.1 Primary Reformer
Primary Reformer
T1 = 314 oC T3 = 828
TREF = 300 oC
o
C
C8H18 = 68092.60
mole/hr
C8H18 = 680926.05 mole/hr H2 = 12256670 mole/hr
CO = 4765928.6 mole/hr
T2 = 300 oC CO2 = 185901.8 mole/hr
ΔH + ΔEk + ΔEp = Q – W
As, no moving parts and equipment is not at height and external work is not going to
taking place so kinetic and potential energy terms can also be neglected.
Q = ΔH
Q = HOUT - HIN
Q = {68092.60 [Hf C8H18 + HC8H18]} - {680926.05 [Hf C8H18 + HC8H18]} + {6128333.3 [H f H2O
+ HH2O]} – {12256670 [H f H2 + HH2]} – {4765928.6[H f CO + HCO]} – {185901.8[ H f CO2 +
HCO2]}
Heat of Formation:
Hf C8H18(g) = -208.4 KJ/mole
Hf H2O(g) = -241.83 KJ/mole
Hf H2 =0
Hf CO(g) = -110.52 KJ/mole
Hf CO2(g) = -393.5 KJ/mole
Molar Enthalpy
Using Table B.2 Felder Rousseau 3rd Edition in order to calculate molar enthalpy
H = a + bT + cT2 + dT3
As,
TREF = 468 oC
O2 = 851970.33 mole/hr
N2 = 3277739.2 mole/hr
Q = ΔH
Q = {680.9 [Hf C8H18 + HC8H18]} - {680926.05 [Hf C8H18 + HC8H18]} + {607311.1 [H f H2O +
HH2O]} + {3257739.2 [H f N2 + HN2]} + {310718.1[H f O2 + HO2]} - {3277739.2 [H f N2 +
HN2]} – {851970.33[H f O2 + HO2]} + {540736.4 [H f CO2 + HCO2]}
Molar Enthalpy
Using Table B.2Felder Rousseau 3rd Edition in order to calculate molar enthalpy
H = a + bT + cT2 + dT3
TREF = 300 oC
T1 = 314 oC T2 = 434 oC
CO = 1.429x106 mole/hr
CO = 4.765x106 mole/hr H2O = 1.392x106
mole/hr
H2 = 3.387x106 mole/hr
T2 = 300 oC CO2 = 3.345x106 mole/hr
Q = ΔH
Putting all values from Table B.1 and B.2 Felder Rousseau 3rd Edition. We get,
LTSC
TREF = 230 oC
T3 = 240 oC T1 = 217 oC
CO = 1.429x104 kmole/hr
CO = 1.429x106 kmole/hr
CO2 = 1.42x106
kmole/hr
T2 = 230 oC H2 = 1.423x106 kmole/hr
H2O = 6797.22 kmole/hr
Q= ΔH
Putting all the values from table B.1 and B.2 Felder Rousseau 3rd Edition. We get,
4.5 Methanator
T3 = 347 oC
T1 = 316 oC METHANATOR
TREF = 316 oC
CO = 400.34 Kg/hr
CH4= 313.45
Kg/hr
H2O= 455.03
Kg/hr
T2 = 318 oCH2= 34005.54 Kg/hr
CO= 4 Kg/hr
CO2= 2.42 Kg/hr
Q = {313.45 [Hf CH4 + HCH4]} - {239.18 [H f CO2 + HCO2]} - {396.34[H f CO + HCO]} - {128.5
[H f H2 + HH2]}
- {455.03 [H f H2O + HH2O]}
Putting all values, using Table B.1 and B.2 Felder Rousseau 3rd Edition. We get,
4.6 Convertor
CONVERTOR
TREF = 250 oC
T1 = 250 oC
H2 = 19546.44 Kg/hr
NH3=
110834.4 Kg/hr
N2=
1824.33Kg/hr
NH3= 110834.4
Kg/hr
H2= 390.93 Kg/hr
Putting all values, using Table B.1 and B.2 Felder Rousseau 3rd Edition. We get,
Q = - 300867521 KJ/hr
REFERENCES
3- “Plant design and Economics for Chemical Engineers” by Max S. Peters and
Klaus D. Timmerhaus