PAPER INDUSTRI PETRO DAN OLEOKIMIA

UREA

DIAN ANGGRAINI PURBA

1107114263
CLASS B

CHAPTER I
INTRODUCTION
The application of the Best Available Techniques (BAT) concept as per the EU
Directive on Integrated Pollution Prevention and Control (IPPC) requires
emissions into air, water and to land to be prevented. Where this is not practicable
the emissions should be minimised by the use of recovery and recycling
techniques with due account being given to the efficient use of energy and
material resources. This Booklet describes the production processes for urea and
urea ammonium nitrate (UAN) and the associated emissions. The Booklet does
not give a detailed description of all the different processes in operation or
available from technology suppliers. Any process which can meet the emission
figures given in Chapter 8 should be considered as BAT. Urea is the major end
product of nitrogen metabolism in humans and mammals. Ammonia, the product
of oxidative deamination reactions, is toxic in even small amounts and must be
removed from the body. The urea cycle or the ornithine cycle describes the
conversion reactions of ammonia into urea. Since these reactions occur in the
liver, the urea is then transported to the kidneys where it is excreted.

CHAPTER II
CONTENT
Urea (NH2CONH) is of great importance to the agriculture industry as a nitrogenrich fertiliser. In Kapuni, Petrochem manufacture ammonia and then convert the
majority of it into urea. The remainder is sold for industrial use.
Ammonia synthesis
Ammonia is synthesised from hydrogen (from natural gas) and nitrogen (from the
air). Natural gas contains some sulfurous compounds which damage the catalysts
used in this process. These are removed by reacting them with zinc oxide, e.g.
ZnO + H2S ZnS + HO
The methane from the natural gas is then converted to hydrogen:
CH4 + H2O
CH4 + 2H2O
CO + H2O

3H + CO
4H2 + CO2
H2 + CO2

Air is mixed in with the gas stream to give a hydrogen:nitrogen ratio of 3:1.
Water, carbon monoxide and carbon dioxide (all of which poison the iron catalyst
used in the ammonia synthesis) are removed. The carbon monoxide is converted
to carbon dioxide for use in urea production, and the carbon dioxide removed:
CO + H2O CO2 + H2
The remaining traces of CO and CO2 are converted to methane and then
the gases cooled until the water becomes liquid and can be easily removed. The

nitrogen and hydrogen are then reacted at high temperature and pressure using an
iron catalyst to form ammonia:
N2 + 3H2

2NH3

Urea synthesis
Urea is made from ammonia and carbon dioxide. The ammonia and carbon
dioxide are fed into the reactor at high pressure and temperature, and the urea is
formed in a two step reaction
2NH3 + CO2 NH2COONH4 (ammonium carbamate)
NH2COONH4 H2O + NH2CONH2 (urea)
The urea contains unreacted NH3 and CO2 and ammonium carbamate. As
the pressure is reduced and heat applied the NH2COONH4 decomposes to NH3
and CO2. The ammonia and carbon dioxide are recycled. The urea solution is then
concentrated to give 99.6% w/w molten urea, and granulated for use as fertiliser
and chemical feedstock. Ammonia and urea are two chemicals which are very
important to the New Zealand economy. This article covers a process used by
Petrochem in Kapuni, South Taranaki, to synthesise ammonia from natural gas
and air, then synthesise urea from this ammonia and carbon dioxide. Annually 105
000 tonnes of pure ammonia (300 T day-1) are produced in Kapuni, and most of
this is converted to urea. Currently 182 000 tonnes of granular urea are produced
annually (530 T day-1), but this is soon expected to increase to 274 000 tonnes.
Uses of ammonia and urea
As has been stated above, most of the ammonia is used on site in the
production of urea. The remainder is sold domestically for use in industrial
refrigeration systems and other applications that require anhydrous ammonia. The
urea is used as a nitrogen-rich fertiliser, and as such is of great importance in
agriculture, one of New Zealand's major industries. It is also used as a component
in the manufacture of resins for timber processing and in yeast manufacture.

THE AMMONIA MANUFACTURING PROCESS

Ammonia is produced in a process known as the Haber process, in which
nitrogen and hydrogen react in the presence of an iron catalyst to form ammonia.
The hydrogen is formed by reacting natural gas and steam at high temperatures
and the nitrogen is supplied from the air1. Other gases (such as water and carbon
dioxide) are removed from the gas stream and the nitrogen and hydrogen passed
over an iron catalyst at high temperature and pressure to form the ammonia. The
process is shown schematically in Figure 1.
Step 1 - Hydrogen production
Hydrogen is produced by the reaction of methane with water. However,
before this can be carried out, all sulfurous compounds must be removed from the
natural gas to prevent catalyst poisoning. These are removed by heating the gas to
400oC and reacting it with zinc oxide:
ZnO + H2S ZnS + H2O
Following this, the gas is sent to the primary reformer for steam reforming,
where superheated steam is fed into the reformer with the methane. The gas
mixture heated with natural gas and purge gas to 770oC in the presence of a nickel
catalyst. At this temperature the following equilibrium reactions are driven to the
right, converting the methane to hydrogen, carbon dioxide and small quantities of
carbon monoxide:
CH4 + H2O 3H2 + CO
CH4 + 2H2O 4H2 + CO2
CO + H2O H2 + CO2
This gaseous mixture is known as synthesis gas.
Step 2 - Nitrogen addition
The synthesis gas is cooled slightly to 735oC. It then flows to the
secondary reformer where it is mixed with a calculated amount of air. The highly
exothermic reaction between oxygen and methane produces more hydrogen.
Important reactions are:
CO + H2O CO2 + H2

O2 + 2CH4 2CO + 4H2

O2 + CH4 CO2 + 2H2

2O2 + CH4 ! 2H2O + CO2

In addition, the necessary nitrogen is added in the secondary reformer. As the
catalyst that is used to form the ammonia is pure iron, water, carbon dioxide and
carbon monoxide must be removed from the gas stream to prevent oxidation of
the iron. This is carried out in the next three steps.

Step 3 - Removal of carbon monoxide

Here the carbon monoxide is converted to carbon dioxide (which is used
later in the synthesis of urea) in a reaction known as the water gas shift reaction:
CO + H2O CO2 + H2
This is achieved in two steps. Firstly, the gas stream is passed over a Cr/Fe 3O4
catalyst at 360oC and then over a Cu/ZnO/Cr catalyst at 210 oC. The same reaction
occurs in both steps, but using the two steps maximises conversion.
Step 4 - Water removal
The gas mixture is further cooled to 40oC, at which temperature the water
condenses out and is removed.
Step 5 - Removal of carbon oxides
The gases are then pumped up through a counter-current of UCARSOL TM
solution (an MDEA solution, see article). Carbon dioxide is highly soluble in
UCARSOL, and more than 99.9% of the CO 2 in the mixture dissolves in it. The
remaining CO2 (as well as any CO that was not converted to CO 2 in Step 3) is
converted to methane (methanation) using a Ni/Al2O3 catalyst at 325oC: 2
CO + 3H2 CH4 + H2O
CO2 + 4H2 CH4 + 2H2O
The water which is produced in these reactions is removed by
condensation at 40oC as above. The carbon dioxide is stripped from the
UCARSOL and used in urea manufacture. The UCARSOL is cooled and reused
for carbon dioxide removal.
Step 6 - Synthesis of ammonia

The gas mixture is now cooled, compressed and fed into the ammonia
synthesis loop (see Figure 1). A mixture of ammonia and unreacted gases which
have already been around the loop are mixed with the incoming gas stream and
cooled to 5oC. The ammonia present is removed and the unreacted gases heated to
400oC at a pressure of 330 barg and passed over an iron catalyst. Under these
conditions 26% of the hydrogen and nitrogen are converted to ammonia. The
outlet gas from the ammonia converter is cooled from 220oC to 30oC. This cooling
process condenses more the half the ammonia, which is then separated out. The
2These reactions are the reverse of the primary reformer reactions seen in Step 1.
The catalyst in both cases is nickel, illustrating the fact that a catalyst accelerates
both the forward and back reactions of an equilibrium system. At reforming
temperatures (~850oC) the methane is almost completely converted to carbon
oxides and hydrogen as the reaction is endothermic and favoured by the high
temperature. However, at the much lower temperature used for methanation
(~325oC), the equilibrium lies to the right and practically complete conversion of
the carbon oxides to methane is obtained. I-Chemicals-A-Ammonia and Urea-5
remaining gas is mixed with more cooled, compressed incoming gas. The reaction
occurring in the ammonia converter is:
N2 + 3H2 2NH3
The ammonia is rapidly decompressed to 24 barg. At this pressure,
impurities such as methane and hydrogen become gases. The gas mixture above
the liquid ammonia (which also contains significant levels of ammonia) is
removed and sent to the ammonia recovery unit. This is an absorber-stripper
system using water as solvent. The remaining gas (purge gas) is used as fuel for
the heating of the primary reformer. The pure ammonia remaining is mixed with
the pure ammonia from the initial condensation above and is ready for use in urea
production, for storage or for direct sale. Ammonia product specifications are
given in
Table 2.

Water is not listed among the gases considered because its levels are highly
variable. All water is eliminated after step 4.
All figures are given in mol % (i.e. the percentage of the total number of moles
of gas present that are due to this gas).
*The gaseous composition after Step 4 is the same as that after Step 3 as Step 4 is
simply the removal of water.
Table 2 - Ammonia specifications

THE UREA MANUFACTURING PROCESS

The commercial synthesis of urea involves the combination of ammonia and
carbon dioxide at high pressure to form ammonium carbamate which is
subsequently dehydrated by the application of heat to form urea and water.

Reaction 1 is fast and exothermic and essentially goes to completion under

the reaction conditions used industrially. Reaction 2 is slower and endothermic
and does not go to completion. The conversion (on a CO 2 basis) is usually in the

order of 50-80%. The conversion increases with increasing temperature and

NH3/CO2 ratio and decreases with increasing H2O/CO2 ratio. The design of
commercial processes has involved the consideration of how to separate the urea
from the other constituents, how to recover excess NH3 and decompose the
carbamate for recycle. Attention was also devoted to developing materials to
withstand the corrosive carbamate solution and to optimise the heat and energy
balances. The simplest way to decompose the carbamate to CO 2 and NH3 requires
the reactor effluent to be depressurised and heated.
The earliest urea plants operated on a Once Through principle where the
off-gases were used as feedstocks for other products. Subsequently Partial
Recycle techniques were developed to recover and recycle some of the NH3 and
CO2 to the process. It was essential to recover all of the gases for recycle to the
synthesis to optimise raw material utilisation and since recompression was too
expensive an alternative method was developed. This involved cooling the gases
and re-combining them to form carbamate liquor which was pumped back to the
synthesis. A series of loops involving carbamate decomposers at progressively
lower pressures and carbamate condensers were used. This was known as the
Total Recycle Process. A basic consequence of recycling the gases was that the
NH3/CO2 molar ratio in the reactor increased thereby increasing the urea yield.
Significant improvements were subsequently achieved by decomposing
the carbamate in the reactor effluent without reducing the system pressure. This
Stripping Process dominated synthesis technology and provided capital/energy
savings. Two commercial stripping systems were developed, one using CO2 and
the other using NH3 as the stripping gases. Since the base patents on stripping
technology have expired, other processes have emerged which combine the best
features of Total Recycle and Stripping Technologies. For convenience total
recycle processes were identified as either conventional or stripping
processes.
The urea solution arising from the synthesis/recycle stages of the process
is subsequently concentrated to a urea melt for conversion to a solid prilled or
granular product. Improvements in process technology have concentrated on

reducing production costs and minimising the environmental impact. These

included boosting CO2 conversion efficiency, increasing heat recovery, reducing
utilities consumption and recovering residual NH3 and urea from plant effluents.
Simultaneously the size limitation of prills and concern about the prill tower offgas effluent were responsible for increased interest in melt granulation processes
and prill tower emission abatement. Some or all of these improvements have been
used in updating existing plants and some plants have added computerised
systems for process control. New urea installations vary in size from 800 to
2,000t.d-1 and typically would be 1,500t.d-1 units. Modern processes have very
similar energy requirements and nearly 100% material
efficiency. There are some differences in the detail of the energy balances but they
are deemed to be minor in effect. Block flow diagrams for CO2 and NH3
stripping total recycle processes are shown in Figures 1 and 2.

Urea Plant Installations in Europe

62 urea plants are in operation in Western Europe in the year 2000. The total
capacity in the fertilizer year 1999/2000 is about 5.8 million tonnes.
Description of BAT Production Processes
The process water from each process discussed in this section is purified by
recovery of dissolved urea, NH3 and CO2 which are recycled to the synthesis
section via a low pressure carbamate condensation system.
Carbon dioxide stripping process
NH3 and CO2 are converted to urea via ammonium carbamate at a
pressure of approximately 140bar and a temperature of 180-185C. The molar

NH3/CO2 ratio applied in the reactor is 2.95. This results in a CO2 conversion of
about 60% and an NH3 conversion of 41%. The reactor effluent, containing
unconverted NH3 and CO2 is subjected to a stripping operation at essentially
reactor pressure, using CO2 as stripping agent. The strippedoff NH3 and CO2 are
then partially condensed and recycled to the reactor. The heat evolving from this
condensation is used to produce 4.5bar steam some of which can be used for
heating purposes in the downstream sections of the plant. Surplus 4.5bar steam is
sent to the turbine of the CO2 compressor. The NH3 and CO2 in the stripper
effluent are vaporised in a 4bar decomposition stage and subsequently condensed
to form a carbamate solution, which is recycled to the 140bar synthesis section.
Further concentration of the urea solution leaving the 4bar decomposition stage
takes place in the evaporation section, where a 99.7% urea melt is produced.
Ammonia stripping process
NH3 and CO2 are converted to urea via ammonium carbamate at a
pressure of 150bar and a temperature of 180C. A molar ratio of 3.5 is used in the
reactor giving a CO2 conversion of 65%. The reactor effluent enters the stripper
where a large part of the unconverted carbamate is decomposed by the stripping
action of the excess NH3. Residual carbamate and CO2 are recovered downstream
of the stripper in two successive stages operating at 17 and 3.5bar respectively.
NH3 and CO2 vapours from the stripper top are mixed with the recovered
carbamate solution from the High Pressure (HP)/Low Pressure (LP) sections,
condensed in the HP carbamate condenser and fed to the reactor. The heat of
condensation is used to produce LP steam. The urea solution leaving the LP
decomposition stage is concentrated in the evaporation section to a urea melt.
Prilling
In urea fertilizer production operations, the final product is in either prilled
or granular form. Production of either form from urea melt requires the use of a
large volume of cooling air which is subsequently discharged to the atmosphere. A
block diagram of the prilling and granulation processes is shown in Figure 3. The
concentrated (99.7%) urea melt is fed to the prilling device (e.g. rotating
bucket/shower

type spray head) located at the top of the prilling tower. Liquid droplets are
formed which solidify and cool on free fall through the tower against a forced or
natural up-draft of ambient air. The product is removed from the tower base to a
conveyor belt using a rotating rake, a fluidised bed or a conical hopper. Cooling to
ambient temperature and screening may be used before the product is finally
transferred to storage. The design/operation of the prilling device exerts a major
influence on product size. Collision of the molten droplets with the tower wall as
well as inter-droplet contact causing.

agglomeration must be prevented. Normally mean prill diameters range from 1.62.0mm for prilling operations. Conditioning of the urea melt and crystal seeding
of the melt, may be used to enhance the anti-caking and mechanical properties of
the prilled product during storage/ handling.
Granulation
Depending on the process a 95-99.7% urea feedstock is used. The lower
feedstock concentration allows the second step of the evaporation process to be
omitted and also simplifies the process condensate treatment step. The basic
principle of the process involves the spraying of the melt onto recycled seed
particles or prills circulating in the granulator. A slow increase in granule size and
drying of the product takes place simultaneously. Air passing through the
granulator solidifies the melt deposited on the seed material. Processes using low
concentration feedstock require less cooling air since the evaporation

of the additional water dissipates part of the heat which is released when the urea
crystallizes from liquid to solid. All the commercial processes available are
characterised by product recycle, and the ratio of recycled to final product varies
between 0.5 and 2.5. Prill granulation or fattening systems have a very small
recycle, typically 2 to 4%. Usually the product leaving the granulator is cooled
and screened prior to transfer to storage. Conditioning of the urea melt prior to
spraying may also be used to enhance the storage/handling characteristics of the
granular product.

CHAPTER III
CONCLUSION
Ammonia is synthesised from hydrogen (from natural gas) and nitrogen
(from the air). Natural gas contains some sulfurous compounds which damage the
catalysts used in this process. The commercial synthesis of urea involves the
combination of ammonia and carbon dioxide at high pressure to form ammonium
carbamate which is subsequently dehydrated by the application of heat to form
urea and water. Urea is the major end product of nitrogen metabolism in humans
and mammals.

The process uses three main raw materials: natural gas, air and

water. Petrochems plant is situated adjacent to the Kapuni gas treatment plant so
natural gas is readily accessible. Natural gas is used for both fuel gas and as a
source of carbon dioxide and hydrogen for the process. Air is, of course, in
abundant supply. Water is pumped from the nearby Waingongoro stream for head
water to the boilers, cooling water and process water. This water is treated after
exiting the process and returned to the stream. Thus all raw materials are cheap
and readily available

REFERENCES
Anonim, 2011, Urea Cycle, http://Urea Cycle.htm
Ave, E van Nieuwenhuyse 4, 2000, Production Of Urea And Urea Ammonium
Nitrate
Pangestu, 2008, Industri urea, http : // chemistryismyworld. blogspot . com /
2011 / 03 / industri-urea.html
Fatimah,

Siti Soja, 2011, Industri Pupuk, http://file.upi.edu/Direktor

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AH/Ki mia_industri/INDUSTRI_PUPUK.pdf