CHAPTER NO. 1.

0 1 INTRODUCTION

CHAPTER – 1
INTRODUCTION

1.1 INTRODUCTION:

Ammonia is the most important nitrogenous compound, which is used in the manufacture of
different fertilizers like urea and diammonium phosphate (DAP).

Anhydrous ammonia is commercially prepared by Haber process. In this process, definite volumes of
hydrogen and nitrogen gases are reacted catalytically under specific conditions of temperature,
pressure and concentration in a specially designed reactor called converter as per following reaction.

½ N2(g) + 3/2 H2(g) <==========> NH3(g) H12 oC = -46 KJ Mol-1

The source of nitrogen is air and that of hydrogen is natural gas and steam. Hence air, water,
hydrocarbon (Natural gas or Naphtha etc.) and power are the usual raw materials at ammonia
plant. FFBL ammonia plant is designed by Bechtel for name plate capacity of 1270 MTPD of liquid
ammonia. The design and operational philosophy of the plant was based on the concept of dual
train manufacturing facility. It has a single train front end and a dual train back end with two
synthesis gas compressors. The ammonia plant has attained the capacity of 1570 MTPD of liquid
ammonia subsequent to revamp and several de-bottlenecking projects in 2007.

In the manufacture of ammonia the following chain of operations is carried out:

 Desulphurization of Natural Gas.
 Steam – Methane Reforming.
 CO Shift Conversion
 CO2 Removal System.
 Synthesis gas compression
 Ammonia Synthesis.
 Refrigeration of Product Ammonia.
 Hydrogen and Ammonia Recovery.
 Steam Generation.

This section of manual covers a brief introduction of steps like Natural Gas Desulfurization, Steam-
Methane Reforming, CO Shift Conversion and Steam Generation. These steps, in general, can be
defined as raw synthesis gas preparation steps.

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 CHAPTER NO. 1.0 2 INTRODUCTION

1.2 Desulphurization of Natural Gas:

The Sulphur contents of natural gas is a severe poison to catalysts used in different catalytic
reactions during ammonia manufacturing. So high quality Desulphurized natural gas is used as
feedstock at ammonia plant.

The sulphur compound can be removed from the natural gas feed stock by physical absorption,
adsorption, or chemisorptions on some kind of catalyst surface. Two systems have been used
worldwide to remove undesirable sulphur bearing compounds in Natural gas feed and to protect
the expensive downstream catalysts.

1.2.1 Activated Carbon

In the past it was considered that physical absorption was the only way to adhere sulphur
compounds to the surface of a solid catalyst. Therefore, activated carbon was considered the most
suitable catalyst for desulphurization of Natural gas. Thus cold activated carbon system was used
in older generation plants, as was being done in original design of FFBL ammonia plant.

1.2.2 Hydrodesulphurization
In this process, organic sulphur compounds of natural gas are hydrogenated with Cobalt
molybdenum (CoMo) catalyst at elevated temperature to H2S, which is absorbed on hot ZnO
catalyst bed as indicated below:

R – CH2 – SH + H2  R – CH3 + H2S

ZnO + H2S  ZnS + H2O

1.3 STEAM – METHANE REFORMING

The reforming of natural gas utilizes two simple reversible reactions:

1) Steam-methane reforming

CH4 + H2O <==========> CO + 3H2 H = +206 KJ Mol-1

2) Water gas shift reaction

CO + H2O <==========> CO2 + H2 H = -41 KJ Mol-1

Steam methane reforming reaction is first order in methane and strongly endothermic. So the
forward reaction is favoured by high temperature as well as by low pressure.

The water gas shift reaction is exothermic and is favoured by low temperature but is largely
unaffected by changes in pressure.

To maximize the over all efficiency of conversion of carbon to carbondioxide and the production of
hydrogen, steam-methane reforming is carried out in the presence of catalyst at high temperature
and pressure. The over all reaction by combining the above equations is

CH4 +2H2O --------------- CO2+4H2

It can be seen that with methane the stoichiometric requirement for steam per carbon atom is 1.0
in reforming reaction. But this is not practicable because all catalysts so far developed tend to
promote carbon forming reactions under steam reforming conditions. These reactions can only be
suppressed by using an excess of steam. Therefore, steam to carbon ratios of 3.0 – 3.5 are
commonly used. The excess of steam also promotes reforming reaction. Too high steam to carbon
ratio is also not economical because excess steam acts as heat carrier.

The reforming process in an ammonia plant is divided into two stages i.e. primary reforming and
secondary reforming.

The necessary heat for reaction in primary reformer is supplied as indirect heat by combustion of
natural gas used as fuel. In secondary reformer, heat is supplied as direct heat by mixing process
air into the process gasses. Combustion of process gas provides heat for this second part of
reforming. The mixing of process air in process gas also provides nitrogen required for reaction of
ammonia production and the process air flow is so adjusted that

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 CHAPTER NO. 1.0 3 INTRODUCTION

3:1 Hydrogen to nitrogen ratio in the synthesis gas is achieved.

Nickel based catalyst is used in both primary and secondary reformers.

1.4 CO SHIFT CONVERSION (WATER GAS SHIFT REACTION)

Shift conversion is the conversion of carbon monoxide to carbon dioxide by water gas shift reaction
as under:

CO + H2O <==========> CO2 + H2 H = - 41 KJ Mol-1

The equilibrium of the reaction is independent of pressure. As reaction is exothermic, high

conversions are favoured at low temperature but rate of reaction increases as the temperature is
raised.

The rate of conversion consequently increases with the temperature but decreases when gas
composition is close to equilibrium.

The reaction is carried out in two stages for maximum conversion of CO to CO2
i. Shift conversion at high temperature for maximum rate of reaction.
ii. Shift conversion at low temperature for maximum conversion.

The steam consumption for water gas shift reaction in two stages is less & the conversion is more
economical than that in single stage. Iron based catalyst is used for high temperature shift reaction
& copper based catalyst is used for low temperature shift reaction.

1.5 STEAM GENERATION

A lot of waste heat is generated from burning of fuel gas in primary reformer and combustion
reaction in secondary reformer. Two-heat recovery systems are employed in the Ammonia plant;
1. Heat recovery from Primary Reformer flue gases.
2. Heat recovery from reformed gas outlet at Secondary Reformer.

1.5.1 Primary Reformer Flue Gases

Reforming is an endothermic reaction. Heat is provided by the burning of Natural Gas for this
endothermic nature of the reforming reaction. Flue gases generated as a result of this burning are
directed towards atmosphere through a series of coils. These coils vary in number and contain
different streams i.e. BFW, process air and process gas for preheating; high pressure steam for
superheating, BFW for steam generation etc. Heat recovery from flue gases is accomplished by
inducing these gases from the furnace and exhausting in the atmosphere with the help of induced
draft fans. In their way to atmosphere theses gases transfer their heat to the coils of convection
section.

1.5.2 Secondary Reformer Outlet

As a result of combustion in both Primary and Secondary Reformers the temperature of resultant
mixture of the gases is increased markedly at the outlet of secondary Reformer. These gases are
to be cooled because all other following reaction like CO shift conversion favor low temperature.

To get these gases cooled down to the desired temperature, a heat recovery system is introduced
at this point. Cooling the gas is one of the most important factors of the system because of the
theoretical risk of carbon formation according to the Boudouard reaction as under:

2CO  CO2 + C

This reaction can only take place at a temperature below 775 oC, because of the thermodynamic
conditions and above 650oC because of the reaction rate, which is too slow to have any practical
importance below this temperature. It is, therefore, important to pass this temperature range
quickly, and contact between gas and any hot surface in this temperature range is avoided.

For this purpose, cooling of the gases is carried out in specially designed boilers producing high
pressure steam. The boilers are designed to obtain the required cooling. These shell and tube

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CHAPTER NO. 1.0 4 INTRODUCTION

boilers not only produce high pressure steam but also lower down the process gas temperature to
favour the exothermic reaction of shift conversion.

The remaining heat of process gas is also recovered in a BFW heater, E-205 and a low pressure
steam boiler, [Link] BFW after being heated in E-205 is sent to steam generation system of
reformers and LS produced in E-2002 is used as heat input for CO2 removal system.

AREA SPECIFIC COURSE – REFORMING & CO CONVERSION