School of Science and Engineering

BEng Chemical Engineering

April 2014

Design Project:
Design of a fertiliser plant producing Urea and
Ammonium Sulphate from Ammonia

Muhammad Nawaz

Supervisor

David Peel

Abstract
Production of fertilisers is a vital industry to sustain an ever growing international population.
This report considers and evaluates different processes to produce ammonium sulphate and
urea from a feed of ammonia and proposes an outline design of a large scale production
facility using the most cost effective process. The design brief is to produce urea and
ammonium sulphate according to a split ratio of 60:40 with using a basis of 550,000
tonnes/year of ammonia. The plant must also have the ability to alter the production ratio
according to a deviation of 10% for both products. Based on the profitability, the report
concludes that the most cost effective route of satisfying the design brief was to produce urea
from carbon dioxide using the Snamprogetti design and ammonium sulphate from sulphuric
acid. The total cost to build the plant will be 268.68 Million with payback time of 4.1 years
but using Taylors method gave a payback time of 2.5years.

Detail mechanical and chemical design of urea reactor was carried. The volume of the
isothermal plug flow, pseudo 1st order reactor was found to be 145.5m3 with length of 27m
and diameter of 2.61m with residence time of 16.71seconds. Reactor thickness of 100mm
was obtained to withstand higher operating conditions. Half pipe cooling jacket was used to
maintain the reactor isothermal conditions. The cost of the urea plant was a found to be
4855059.7 which is well in the range of current industrial urea reactor cost. HAZOP was
carried to identified the hazards and actions/safeguards needed to prevent reactor. LOPA was
carried out on one of the HAZOP node in order to find the Safety Integrity Level (SIL) and
finally current industrial issues were discussed in order to transfer data from HAZOP to
LOPA and recommendations were made to satisfy the clients criteria.

Acknowledgement
I would sincerely like to express my gratitude to my supervisor David Peel for the continuous
support of my dissertation and research, for his patient and immense knowledge. I could not
imagine having a better supervisor and mentor for my project. My sincere thanks also go to
Dr Samatha Gooneratne, Professor Maria Olea and Dr Paul Russell who provided me
guidance whenever I needed. I would like to thanks to all my friends who supported me and
incented me to strive towards my goal.

Very special thanks go to my parents and my elder brother who gave me financial support
and always encourage me to study and work hard during my time in England.

Table of Contents
Abstract .....................................................................................................................................................
Acknowledgement ................................................................................................................................... i
Group Report .......................................................................................................................................... 1
1.1 Introduction ............................................................................................................................... 1

i
 1.2 Project brief ............................................................................................................................... 1
1.3 Possible routes ........................................................................................................................... 1
1.4 Process Description for Urea ..................................................................................................... 2
1.5 Process Description for Ammonium Sulphate ........................................................................... 2
1.6 Process One ............................................................................................................................... 3
1.7 Overall Mass Balance for Urea................................................................................................... 3
1.8 Overall mass balance for Ammonium Sulphate......................................................................... 4
1.9 Process 2 .................................................................................................................................... 5
1.10 Overall mass balance for Urea............................................................................................... 5
1.11 Overall mass balance for Ammonium Sulphate .................................................................... 5
1.12 Cost Analysis .......................................................................................................................... 6
1.13 Profitability of process 1 ........................................................................................................ 6
1.14 Profit for Process 2 ................................................................................................................ 7
1.15 Product Sensitive Analysis (production changes effect capital) ............................................ 8
1.16 Capital Cost and Payback time .............................................................................................. 8
1.17 Environmental and Sustainability .......................................................................................... 9
1.18 Discussion of selection process ........................................................................................... 11
1.19 Preferred route .................................................................................................................... 11
2 Detailed Mass Balances ................................................................................................................ 11
2.1 Urea Production Mass Balance ................................................................................................ 11
2.2 Ammonium Sulphate Production Mass Balance ..................................................................... 12
3 Detailed Energy Balances .............................................................................................................. 13
3.1 Energy Balance on Urea Plant .................................................................................................. 14
3.2 Urea reactor ............................................................................................................................. 14
3.2.1 Stream enthalpy of Ammonium carbamate recycle stream ........................................... 15
3.2.2 Stream enthalpy of CO2+NH3 recycled stream from decomposers ............................... 15
3.2.3 Total stream enthalpies of inlet streams ........................................................................ 15
3.2.4 Stream enthalpy of outlet stream ................................................................................. 15
3.2.5 Heat duty of the reactor.................................................................................................. 15
3.3 Stripper .................................................................................................................................... 16
3.4 Decomposers ........................................................................................................................... 16
3.4.1 Medium pressure decomposer ....................................................................................... 16
3.4.2 Low pressure decomposer .............................................................................................. 16
3.5 Evaporator ............................................................................................................................... 16

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 3.5.1 1st Evaporator ................................................................................................................. 16
3.5.2 2nd Evaporator................................................................................................................ 17
3.6 Prilling Tower ........................................................................................................................... 17
Ammonium Sulphate Energy Balance ................................................................................................... 17
3.7 The Reactor energy balance for ammonium sulphate crystalliser (reactor): ........................... 17
3.8 Filter and Sump tank ................................................................................................................ 18
3.9 Dryer ........................................................................................................................................ 19
Pinch Technology .................................................................................................................................. 19
Summary ............................................................................................................................................... 20
4 Individual Design Part ................................................................................................................... 20
Urea Reactor Chemical Design .......................................................................................................... 20
4.1 Introduction ............................................................................................................................. 20
4.2 Overall mass balance ............................................................................................................... 20
4.3 Mass transfer Aspects .............................................................................................................. 21
4.4 Reactor Volume ....................................................................................................................... 21
4.4.1 1st Approach .................................................................................................................... 21
4.4.2 2nd Approach ................................................................................................................... 23
4.4.3 3rd Approach .................................................................................................................... 24
4.5 Optimum Conditions ................................................................................................................ 26
4.6 Residence Time ........................................................................................................................ 27
4.7 Cooling Jacket .......................................................................................................................... 27
4.8 Factors effecting urea process ................................................................................................. 28
4.8.1 Effect of the reactor outlet temperature on the product yield ...................................... 28
4.8.2 Effect of Pressure ............................................................................................................ 28
4.8.3 Reactant concentration effect ........................................................................................ 28
4.9 Sieve Plates (dimensions i.e. sizing) ......................................................................................... 29
Conclusion ............................................................................................................................................. 29
5 Mechanical Design........................................................................................................................ 29
5.1 Introduction ............................................................................................................................. 29
5.2 Classifications of pressure vessel ............................................................................................. 30
5.3 Pressure vessel codes and standards....................................................................................... 30
5.4 Reactor vessel design consideration........................................................................................ 30
5.5 Material of construction ........................................................................................................... 30
5.6 Reactor operating conditions ................................................................................................... 32

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 5.7 Reactor vessel load calculations .............................................................................................. 32
5.8 Reactor wall thickness calculations ......................................................................................... 33
5.9 Heads and closures .................................................................................................................. 33
5.9.1 Hemispherical head thickness calculations..................................................................... 33
5.9.2 Diameter/length calculations .......................................................................................... 33
5.10 Combine loading .................................................................................................................. 34
5.11 Stress analysis ...................................................................................................................... 34
5.11.1 Longitudinal Stress ..................................................................................................... 34
5.11.2 Circumferential stress ................................................................................................. 34
5.11.3 Direct or dead weight stress ........................................................................................ 34
5.11.4 Bending stress ............................................................................................................. 35
5.11.5 Total longitudinal stress .............................................................................................. 35
5.12 Dead weight of vessel .......................................................................................................... 36
5.12.1 Weight of the plates .................................................................................................... 36
5.12.2 Insulation weight......................................................................................................... 37
5.12.3 Total weight ................................................................................................................ 37
5.12.4 Dynamic wind pressure .............................................................................................. 37
5.13 Vessel support ..................................................................................................................... 37
5.14 Skirt thickness ...................................................................................................................... 38
6 Eccentric load ................................................................................................................................ 39
6.1 Cooling jacket ........................................................................................................................... 40
6.2 Heat transfer coefficient (hi) at reactor outer wall ................................................................. 40
6.3 Pressure drop across tube () ............................................................................................ 42
7 Pipe Sizing and pressure drop ....................................................................................................... 43
8 Flanges .......................................................................................................................................... 44
Conclusion ............................................................................................................................................. 45
9 Engineering Design........................................................................................................................ 45
10 Design Specifications ............................................................................................................... 46
11 Costing ..................................................................................................................................... 46
11.1 Introduction ......................................................................................................................... 46
11.2 Factorial method of cost estimation ................................................................................... 47
11.3 Major equipments items ..................................................................................................... 48
11.4 Scale up Method .................................................................................................................. 50
Conclusion ............................................................................................................................................. 51

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12 Heath Safety and Environment (HSE) ...................................................................................... 51
12.1 Safety ................................................................................................................................... 51
12.2 HAZOP and P&ID.................................................................................................................. 54
12.3 Process control and Instrumentation Diagram..................................................................... 55
13 Plant Layout ............................................................................................................................. 57
13.1 Industrial land prices and site selection: .............................................................................. 57
13.2 Plant Layout and other consideration ................................................................................. 58
13.3 Plant emergency shutdown and start-up Procedure .......................................................... 58
14 (LOPA) Layer of Protection Analysis......................................................................................... 59
14.1 Current Industrial Problems in using HAZOP/LOPA interface ............................................. 60
Overall Conclusion ................................................................................................................................ 61
References ............................................................................................................................................ 63
Appendix1: Plant Layout and Process 2 (Urea (Stamicarbon) and ammonium sulphate using gypsum
.............................................................................................................................................................. 66
Appendix 2: Decision Analysis and DOW Index for Fire and Explosion ................................................ 67
Appendix3: Urea and Ammonium Sulphate plant PFD, capital cost and Payback time ....................... 68
Appendix 4 : Mass flow and Energy Flow table for Urea and Ammonium Sulphate Plant .................. 69
Appendix 5: LOPA terms explanations and method of calculations for SIL .......................................... 71
Appendix 6: SIL calculations for one of the HAZOP node. .................................................................... 72
Appendix 7 : PFDs for required SIL, Colour coded HAZOP diagram, Residence time Calculations....... 73
Appendix 8: Full HAZOP Analysis .......................................................................................................... 74
Appendix 9: HAZOP to LOPA data transfer, Mechanical/chemical safety sheet .................................. 78

Figure 1: total profit obtained using both methods ............................................................................... 8

Figure 2: Pinch Technology for urea and ammonium sulphate plant................................................... 19
Figure 3: Location of the reaction in the liquid film (Octave, 1999) ..................................................... 21
Figure 4: Effect of pressure on volume of............................................................................................. 26
Figure 5: Effect of ammonia and carbon dioxide feed ration on residence time ................................. 27
Figure 6: stresses due to dead weight load .......................................................................................... 35
Figure 7: Stresses in cylinder under combine loading .......................................................................... 36
Figure 8: skirt support and skirt support design ................................................................................... 38
Figure 9: Heat transfer coefficient from the reactor outer wall with respect to coolant velocity ...... 42
Figure 10: Specific heat (Ks) of CO2 Vs. pressure ................................................................................. 50
Figure 11: CO2 compressibility (Zs) vs. pressure .................................................................................. 50
Figure 12: P&ID for urea reactor after HAZOP ...................................................................................... 56
Figure 13: Land prices in England ......................................................................................................... 58
Figure 14: Independent Protection Layers ........................................................................................... 59

v
Table 1: Total ammonia and plant working days per year in case of shut down. .................................. 1
Table 2: Overall mass balance of urea plant ........................................................................................... 4
Table 3: Overall mass balance for ammonium sulphate plant ............................................................... 4
Table 4: overall mass balance for Urea production (Stamicarbon process) ........................................... 5
Table 5: Overall mass balance in kg/year for ammonium sulphate production..................................... 6
Table 6: total raw material cost and selling price of the products ......................................................... 7
Table 7: Raw material and products cost and calculation for profitability............................................. 7
Table 8: Payback time using shortcut method........................................................................................ 9
Table 9: IChemE matrix calculations for different components ........................................................... 10
Table 10: Operating conditions for urea reactor ................................................................................. 14
Table 11: Flow of material across reactor............................................................................................. 20
Table 12: Heat capacity of water .......................................................................................................... 28
Table 13: shows the advantages and disadvantages of different materials of constructions. ............ 31
Table 14: Design operating conditions and material of constructions ................................................. 32
Table 15: total weight of vessel ............................................................................................................ 37
Table 16: physical properties of water and other dimension less parameter ...................................... 41
Table 17: Typical velocities and allowable pressure drop (Sinnott & Towler, 2009, p. 259) ................ 43
Table 18: Materials cost factors (fm) relative to the plain carbon steel. Installation factor proposed
by Hand ................................................................................................................................................. 47
Table 19: purchased equipment cost for common plant equipments ................................................. 48
Table 20: Flammability, hazards identification, and PPE for NH3, CO2 and Urea and carbamate ....... 51

vi
1 Group Report
1.1 Introduction
This report will outline the design of multiproduct fertiliser plant producing urea and
ammonium sulphate. The design will consider different possible production routes for each
product, separate costing analysis, payback times for each route and also environmental and
sustainability factors that may affect the plant design along with the surrounding areas and
population. Preferred route will be selected based on the profitability of the two plants. Detail
energy balance and pinch technology will be carried out in order to find where the energy
could be

Table 1: Total ammonia and plant working days per year in case of shut down.

Total ammonia (tonne/year) 550000

Total ammonia (Kg/year) 550000000

Plant working days 300 days

1.2 Project brief

The project specification was an initial proposal to design a fertiliser plant capable of
processing 550,000 tonnes of ammonia per year to produce 60% urea and 40% ammonium
sulphate. A product sensitivity analysis must also be carried out to investigate the
consequences of altering the production ratios by 10%. As the feed material is the same for
both products, it seemed logical to run both processes alongside each other on the same site
looking to overlap any equipment where possible. This may also allow the design to use
energy integration where possible, reducing running costs. Finally, an investigation into the
environment and sustainability factors must be considered.

1.3 Possible routes

As specified in the project brief, the proposed plant must have the capability to produce two
fertiliser products. Due to the possibility of different production routes being available for
each product, the research was divided into two parts, one for the production of urea and the
other for the production of ammonium sulphate.

1
1.4 Process Description for Urea
The Snamprogetti process and Stamicarbon process combined produce over 70% of the
worlds urea, for this reason these are the two methods that will be compared. The two
processes produce urea via the same reaction method; however, the operating conditions and
recycle of the unreacted components differ.

The two step reaction for the production of urea is show in reaction 1 and 2 below. The first
reaction shows the fast exothermic production of ammonium carbamate which then
decomposed in a slow endothermic reaction to form urea.

23 + 2 2 4 (1) 84/

2 4 2 + (2 )2 (2) 23/

The first process route shown in (see appendix 3) is the Snamprogetti process, which differs
from the second process route as it utilises a self-stripping process with ammonia as a
stripping agent. This self-stripping process is a method of recycling the unreacted products
and requires an initial excess of ammonia in the reactor. This is then processed in a stripper
that utilises the excess ammonia and an increased temperature of 210-215oC to revert
ammonium carbamate back to its reactants, carbon dioxide and ammonia (Snamprogetti,
2014, pp. 1-4). These reactants can then be recycled back to the reactor.

The second process route is the Stamicarbon and this process differs from the first as its
reactor conditions are more extreme, requiring up to 200 bar in pressure and in excess of 200
o
C (Stamicarbon, 2014, pp. 11-25). Using these higher operating conditions increases the
operating cost of the process and also increases the initial capital cost of the process. The
Stamicarbon process also utilises a different recycle method, this method involves carbon
dioxide as a stripping agent as opposed to the ammonia used in the first process. In this
counter current stripping process between the reactor product and carbon dioxide, the stripper
conditions are relatively low, reducing the overall operating cost.

1.5 Process Description for Ammonium Sulphate

Lewis Eaton, Abdullah

For the production of the ammonium sulphate, two process routes were researched. Firstly,
the most popular industrially used process involved reaction a feed of gaseous ammonia with
2
a feed of concentrated liquid sulphuric acid as shown in reaction 3 directly in a crystallizer.
This then produced ammonium sulphate crystals that required dewatering in a filtering
centrifuge and finally contacted with hot air in a dryer. The process was carried onto the
comparative costing stage.

23 + 2 4 (4 )2 4 . . (3)

Alternatively, ammonium sulphate can be produced using calcium sulphate, more commonly
known as gypsum. This process requires raw materials of ammonia, carbon dioxide, water
and gypsum. Whilst the main body of the process isnt too dissimilar to the Sulphuric Acid
route, this option would require the raw gypsum lumps to be crushed and grinded before
being used. This obviously would incur greater initial and continuing costs as the process
requires more equipment and has a greater production time. On the other hand, however, the
gypsum supplied in lump form has a much lower purchase cost than sulphuric acid. For this
reason, it was also carried onto the costing stage.

3 + 2 4 (4)

24 + 02 (4 )2 3 + 2 . . (5)

(4 )2 3 + 4 (4 )2 4 + 3 . (6)

In summary of the above process research, it was determined that a costing stage would have
to be carried out to determine the optimum production route for both products. Considering
this, two process routes were formed for the costing stage, named process one and process
two.

1.6 Process One

Process one involves production of urea using Snamprogetti process, and ammonium
sulphate using sulphuric acid as raw material (see appendix 3 for block diagram). This route
was under consideration due to the strong availability of sulphuric acid in the required
quantity, the non-complex plant layout and the low number of different raw materials
required.

1.7 Overall Mass Balance for Urea

(See Nawaz logbook V1, pg. 1-6 for overall mass balances and cost analysis, and profitability
and payback time), Overall reaction for urea production

3
NH3 + CO2 (NH2 )2 CO + H2 O . . (6)

80% of the total ammonia used up for urea production. From the overall reaction equation it
is assumed that 80% of the total ammonia reacted to urea. From reaction 6, CO2 acts as
limiting reactant.

Table 2: Overall mass balance of urea plant

Components Kg/year (inlet) Kg/year (outlet)

NH3 4.4 108 8.81 107

CO2 5.69 108 1.14 108

(NH2 )2 CO 6.21 108

H2 O 1.86 108

Total 1.01 109 1.01 109

1.8 Overall mass balance for Ammonium Sulphate

Muhammad Nawaz

Overall reaction equation

NH3 + 2 4 (4)2 4 . (7)

20% of the total ammonia used up for ammonium sulphate production. Assuming reaction is
100% complete and sulphuric acid acting as limiting reactant according to the balanced
chemical equation.

Table 3: Overall mass balance for ammonium sulphate plant

Components Kg/year (in) Kg/year (out)

NH3 1.1 108 8.81 107
2 4 3.17 108 1.14 108

(4)2 4 4.27 108

Total 4.27 108 4.27 108

4
1.9 Process 2
Process two differs from process one in the respect that ammonium sulphate is produced
using the three-stage route involving ammonia, carbon dioxide, water and gypsum (See
appendix 1 for block diagram). The Stamicarbon route would be used to produce urea, as
opposed to the Snamprogetti route used in process one.

1.10 Overall mass balance for Urea

Muhammad Nawaz

The overall mass balance for urea will be the same as calculated above. Currently two
different methods (Snamprogetti and Stamicarbon) are practising in industries for urea
production but there is no difference in term of calculating overall mass balance.

Table 4: overall mass balance for Urea production (Stamicarbon process)

Components Kg/year (in) Kg/year (out)

NH3 4.4 108 8.81 107
CO2 5.69 108 1.14 108
(NH2 )2 CO 6.21 108
H2 O 1.86 108
Total 1.01 109 1.01 109

1.11 Overall mass balance for Ammonium Sulphate

Muhammad Nawaz

Ammonium sulphate can be produced using gym as given by the balance chemical equation

NH3 + H2 O 4 (8)

24 + 2 (4)2 3 + 2 (9)

(4)2 3 + CaSO4 (NH2 )2 SO4 + CaCO3 . . (10)

Again 20% of the total ammonia used up in producing ammonium sulphate using gypsum. It
is assumed that the first two reactions go to completion 100% and the last reaction goes to
96% completion.

5
Table 5: Overall mass balance in kg/year for ammonium sulphate production

Components Kg/year (in) Kg/year (out)

NH3 1.1 108

H2 O 1.16 108 5.82 107

4 2.26 108 2.26 108

2 1.42 108

(4)2 3 3.11 108 3.23 108

(NH2 )2 SO4 4.1 108

CaCO3 3.11 108

CaSO4 4.4 108 1.76 108

Total 1.35 109 1.35 109

1.12 Cost Analysis

Muhammad Nawaz,

Following the background research into the products and possible process routes, envelope
mass balances were carried out to allow for simple profitability calculations. The equation
used for these calculations can be seen in Figure 8.

Profitability = selling revenue of products cost of raw materials

Other factors need to be considered other than purchase and selling costs; however, it will
give a good early indication of which process should be chosen.

Table 6 and7, shows the purchase and selling costs of all raw materials and products when
using process one as the production route, including the quantity needed. This shows values
of total yearly sales revenue along with total materials cost.

1.13 Profitability of process 1

Muhammad Nawaz,

6
Table 6: total raw material cost and selling price of the products1

Selling price Amount (tonne/year) Sales (/year)

(/tonne)
Products
Urea 215 6.21 108 133 million

Ammonium Sulphate 185 4.27 108 79 million

Total 211.9million
Raw Material
NH3 185 550000 102 million
H2SO4 125 3.17 105 39million

CO2 10 5.69 105 5.7 million

Total 146.7 million
= 211.9 146.7 = 65 million/year

1.14 Profit for Process 2

Muhammad Nawaz

Table 7: Raw material and products cost and calculation for profitability

Selling price Amount (tonne/year) Sales (/year)

(/tonne)
Products
Urea 215 6.21 108 133 million

Ammonium Sulphate 142 4.11 108 58 million

Total 191million
Raw Material
NH3 185 550000 102 million

1
Price of the products and raw materials obtained from a website www.Aliaba.com

7
 70 4.4 105 30.2million
CO2 10 1.42 105 1.4 million
Total 133.6 million
= 191 133.6 = 57.4 million/year

66
64
62

Profit 60
(millions) 58
56
54
52
Process 1 Process 2

Figure 1: total profit obtained using both methods

It can be seen from the above chart that profit made using method 1 (production of
ammonium sulphate using sulphuric acid and urea production by Snamprogetti
process) is 65 million/year while and 57.4 million /year using process 2. Based on
the profitability, process1 is more suitable than process2. In comparison to process one,
process 2, has more equipment and would require more floor area. This would lead to higher
initial and running costs compared to process one.

1.15 Product Sensitive Analysis (production changes effect capital)

The plant is designed for 10% on product composition. This is due to:

Customer demands and market values

Urea production 50-70%

Ammonium Sulphate production 30- 50%

The urea reactor therefore needs to be large enough to process 90% of the
ammonia inlet. The ammonium sulphate reactor therefore needs to be large
enough to process 30% of the ammonia inlet

1.16 Capital Cost and Payback time

Muhammad Nawaz

8
The cost of the urea and ammonium sulphate plant was calculated using shortcut method.

= (/)0.66 . (11)

C = cost of new plant , Cref =cost of existing plant, S= capacity in tonnes per year of
new plant, Sref= capacity in tonnes per year of existing plant (see appendix 3 for detail
calculations)

Table 8: Payback time using shortcut method

Capital Cost (Urea Plant) 261million

Capital Cost Ammonium Sulphate Plant 7.98million

Total Cost 268.68million

Total Payback time 4.1years

To improve the accuracy of the calculated payback time, the Taylor method was used. The
accuracy of this method is closer to 20-30% (Russell, 2013)and reduced the payback time
from 4.1 years to 2.5 years. When calculating the Taylor method, a table is produced where
the major parts of the plant are given values depending on how expensive they are. These
values relate to a score which is summed and an equation is used to calculate their Costliness
index. Putting this value into the final Taylor equation (See Muhammad logbook Volume 1
(2013-2014) pg.20) gave the estimated capital cost of the plant. The total capital cost for the
entire plant is 146.2million which equated to a payback time is 2.5 years.

1.17 Environmental and Sustainability

Abdullah, Megan Jones

The institute of chemical engineers provides a report of sustainability metrics, with the
impact of industry on sustainability being summarised by the tripe bottom line. The triple
bottom line is comprised of the three components, environmental responsibility, economic
return and social development.

For each component of the triple bottom line the report details metrics from which the impact
of the plant can be assessed in a quantitative manner. There are also qualitative points to take
into consideration.

From an economic and environmental aspect it is suggested that the plant proposed be built
and situated in the north east of England, specifically the Teesside area. Land prices in the

9
U.K vary from 240,000 per hectare in the North East to 1.14million in the South East
(Valuation Office Agency, 2011). Due to this variance in land price it is more economically
viable to situate the proposed plant in the North East. To reduce the environmental impact of
the plant it is proposed the plant be built on a current brownfield site. Using a site of land
that has already been developed on reduces the impact on undeveloped land. Additionally
the Teesside area is currently home to large amounts of industry, reducing social stigma
associated with the building of a large scale plant. Also the large amount of industry in the
Teesside means that there is a large population of relevantly skilled workers and that some
issues of plant decommissioning could be avoided as the area has previously been involved in
large scale plant decommissioning.

Ammonia and sulphuric acid used in the process are both hazardous materials therefore the
handling, transportation and storage of these materials is important for both personnel safety
and environmental safety. Due to the large amount of industry within the Teesside area,
sulphuric acid can be sourced locally reducing the transportation time of this hazardous
material which in turn reduces the CO2 produced from transportation. Ammonia is
transported as a liquid and can either be transported in tankers or if a pipe line is built can be
directly transported this way from the ammonia production plant, also reducing CO2
emissions from transport.

Water used in the process is reused in other parts of the process or recycled back into the
system it was previously used in. Other economic benefits of building the proposed plant are
the creation of jobs within the Teesside area.

The quantitative environmental metrics asses the energy, material, water and land used in the
process. For the plant proposed, the following metrics have been calculated.

Table 9: IChemE matrix calculations for different components

Total raw materials used, including 1718782 te/y

packaging

Raw material recycled from other company 1261765 te/y

operations

Raw material used with poses health and 550000 te/y

safety or environmental hazards

10
Total raw materials used per kg of product 2.2 kg/kg

Fraction of raw materials recycled within 0.74 kg/kg

company

Hazardous raw material per kg of product 0.41

Total amount of water used in process 100931281 te/y

1.18 Discussion of selection process

The selection process for deciding with production route to base the build proposal upon is
largely based around the profitability and payback time for the plant. There are other factors
that must be considered such as environmental impacts and sustainable production for the
future, however, the process option which produces a higher profitability is always likely to
become the chosen design.

1.19 Preferred route

The chosen production route after all considerations is process one because of its profit.
Process one involves using the Snamprogetti route to produce urea and reacting ammonia
with sulphuric acid to produce ammonium sulphate.

2 Detailed Mass Balances

Following the decision to use process one as the base for the plant proposal, detailed mass
balances for the production of urea and ammonium sulphate were carried out. In earlier
sections of the report, it was envelope mass balances that were used to calculate profitability
and production rates. Detailed mass balances were carried out as they include important
design aspects such as conversion rates, recovery rates and losses of product due to filtration
and drying, etc.

2.1 Urea Production Mass Balance

(Detail calculations is given in Nawaz logbook Volume1 (2013-2014), pg. 22-26)

Simon Furphy, Muhammad Nawaz

To complete mass balance the general equation for conservation of mass needs to be
considered, =

11
However, if the system is at steady state, as this system is, the balance can be written as,
=

The urea mass balance is based on the three reactions below, the first is the production of
ammonium carbamate from ammonia and carbon dioxide, and this then decomposes to
produce urea which is the required product. The third reaction is the formation of biuret, this
is an unwanted side reaction and the conditions of the reactor are kept so that the production
of this is minimised.

23 + 2 2 4 . . (12)

2 4 (2 )2 + 2 . . (13)

2(2 )2 NH2 CONHCONH2 + NH3 . (14)

It was assumed that 1st reaction goes to 95% completion while 2nd and 3rd reaction goes to
100% completion. From the stoichiometric ratio of reaction 1 given in equation 12, CO2 acts
as a limiting reactant. Using a basis for the reactor outlet and working backward from the
outlet mass percentages it was possible using the equation below to calculate the amount of
moles of carbon dioxide needed. = (( 2) + )/0.95

This takes into account the moles of carbon dioxide used up, as carbon dioxide is the limiting
reactant it can then be used to calculate the moles of ammonia needed for the reaction. To
calculate the recycle streams composition it has been assumed that 100 % of unreacted
components are recycled. Using this assumption a balance around the point at which the
ammonia/carbon dioxide recycle stream mixes with the ammonia/carbon dioxide inlet stream
was completed. From here the inlet stream flow rate can be calculated using the difference
between the recycle stream and reactor inlet stream.

2.2 Ammonium Sulphate Production Mass Balance

Lewis Eaton (logbook) pg. 21-24

A complete stage-by-stage mass balance was carried out for the production of ammonium
sulphate from ammonia and sulphuric acid

12
 23 + 2 4 (4 )2 4 . . (15)

In order to meet the required product split of 60:40, urea to ammonium sulphate, 20% of the
ammonia feed is needed for the production of ammonium sulphate. This results in a total feed
of 110,000tonne/year of ammonia. Based on the plants operational year consisting of 300
days, this equates to a feed of 15,277kg/h of ammonia. Assuming a conversion of 98%, this
means that the amount of ammonia reacted is 14,971kg/h. Given the RMM of ammonia is 17,
this equates to 881kmol/h of reacted ammonia. In accordance with the reaction shown in
equation 15, the ammonia and sulphuric acid feeds react with a stoichiometric ratio of 2:1.
The amount of sulphuric acid reacted is 440kmol/h. There is no excess of either reactant.
Also included with the feed streams is cooling water that is required in the crystalliser due to
the high exothermic nature of the reaction. It is used to maintain constant temperature for the
reaction conditions. The total cooling water used for the reaction is 31,000kg/h, which equals
a molar flow rate of 1715kmol/h. The reaction takes place in the crystalliser and runs at a
98% conversion, as previously stated. According to the reaction in equation 8, the result is
440kmol/h of ammonium sulphate produced. There is a stream from the top of the crystalliser
in which the vaporised cooling water leaves. This contains 50% of the total water inlet and
the 2% of unreacted ammonia. The unused cooling water and 2% unreacted sulphuric acid
are part of the product stream.

The product stream then requires dewatering, as the ammonium sulphate crystals are 67%
w/w of the total mass. The dewatering process is carried out in a filtration centrifuge and
increases the ammonium sulphate to a mass fraction of 95% w/w. Within the centrifuge, a 1%
loss of ammonium sulphate crystals has been accounted for alongside recovery rates for the
water and sulphuric acid of 90% and 98% respectively. These components in the centrifuge
liquid output stream are recycled back to the crystalliser via a sump tank. The recycle of these
materials increases the production of ammonium sulphate slightly, resulting in a 442kmol/h
production rate.

3 Detailed Energy Balances

(Process flow diagrams for urea and ammonium sulphate plants with mass flow rates and total energy
and temperature for each stream are shown in appendix 4)

After completion of the detailed mass balances, energy balances were carried out for the
production of urea and ammonium sulphate. The energy balances are very important to plant

13
design. Obviously, an energy balance shows the points at which energy input is required and
also at any stages in the process at which energy can be recovered. This gives good indication
of running costs for the plant and also aids with plant layout at a later stage. Since energy
integration is an important aspect of this build proposal, it is very beneficial to identify any
process units that can be combined or placed closer together to save money on running costs.

3.1 Energy Balance on Urea Plant

Muhammad Nawaz (Detail calculations is in Nawaz logbook Volume2 (2014), pg1-17)

Energy balance is carried out on urea plant which consists of Reactor, NH3 stripper,
medium/low pressure decomposer, evaporators and prilling tower. Specific heat capacities
and heat of formations were obtained from NIST and Perrys handbook. Heat balance
calculation will be shown by the following. The following assumptions is made

Isothermal reactor, no heat loss across the reactor and reactor is at steady state

3.2 Urea reactor

Table 10: Operating conditions for urea reactor

Reactor outlet and 180C=453K Inlet stream 40C=313K

inside temperature temperature

Recycled Ammonium 180C=453K Datum 25C=298K

Carbamate temperature(T)
Temperature

Reactor operating 140bar

pressure

23 + 2 4 2 (16)

4 2 (2 )2 + 2 . . (17)

Standard heat of reaction was calculated by using the standard enthalpy of formations of
reaction. The equation is shown by the following:

= () ()

Heat of reaction is -42028.6103 kJ/h. The reaction is exothermic at 25oC. As the reactor
operates at 180C, the heat of reaction at 25oC is not applicable. Therefore the enthalpy of the

14
outlet stream and inlet stream are included for the heat of reaction. The enthalpy of the
reaction for the reactor at 180oC with different temperature of the stream is shown below. The
reactor has assumed that the phase of the reactant and the phase of the product do not change.

, = + () () . (18)

() = Where = ( ) . (19)

()=, Where = ( ) . (20)

= + + 2 + 3 + (21), =
2 1000

Specific heat capacities for all components were calculated using formula given in NIST
handbook as follow, where T is in Kelvin; A, B, C, D and E are the heat capacity constant
vary for different components.

3.2.1 Stream enthalpy of Ammonium carbamate recycle stream

Ammonium carbamate was recycled into the urea reactor, the temperature of the ammonium
carbamate stream was assumed at 180C. The calculated stream enthalpy is shown below
(Detail calculations see Nawaz, 2013, P4-7).

( ) = = 94933420.2 /

3.2.2 Stream enthalpy of CO2+NH3 recycled stream from decomposers

Ammonia and CO2 recycled stream coming from decomposers added up into the inlet stream
at temperature of 40C. (2 + 3) = 18169707.3 /

3.2.3 Total stream enthalpies of inlet streams

= = 113103127.5 /

3.2.4 Stream enthalpy of outlet stream

The outlet stream enthalpy is carried out by,() = 143838346/

3.2.5 Heat duty of the reactor

Using the formula given in equation (1) the heat of reaction at 180C is calculated

= 11293392/, It can be seen that the overall reaction is exothermic and this is
the amount of heat produced.

Heat duty of the reactor unit =-11293392.1kJ/hr.

15
3.3 Stripper

Under the condition of high temperature and high pressure, all ammonium carbamate
produced from the reactor has been stripped and recycle to the urea reactor. It was assumed
that there is no phase change happened for ammonium carbamate. The heat duty for this
operating unit is given as below.

= 94933420 /

= 143838346/
= 17945601.83/

3.4 Decomposers
Two decomposer units were used in order to remove NH3 and CO2.

3.4.1 Medium pressure decomposer

= 17945601.8/

3 2 = 1563801 /

, = 96063457/

3.4.2 Low pressure decomposer

= 96063457//

(NH3 + CO2) = 1484371.8 /

=
12512865.9/.

3.5 Evaporator
Two evaporators were used to remove the amount of water from the decomposer product
stream. It was assumed that 70% of water was removed from the 1st evaporator and 77% of
the remaining amount of water was removed from 2nd evaporator. It was assumed that steam
will be used for both evaporators at 147.9C.

3.5.1 1st Evaporator

Amount of steam used to evaporate water can be calculated using the formula

16
 () + 11 = 11 +

1 =Latent heat of vaporization of water=2123.2 kJ/kg (NIST Chemistry WebBook, 2004)

1 = 2614.9/, 1 = 20150.5/ This is the amount of steam needed to

evaporate 70% of water coming from low pressure decomposer.

= 17035.2/

= 10749702.7/

3.5.2 2nd Evaporator

= 1894.5/
, = 415771.5/, 90% of urea was
purified during 1st evaporator and it goes to 97% during 2nd evaporation section.

3.6 Prilling Tower

Urea prill is produced by delivering counter current flow cooling medium (air) into the tower.

Ambient air has been delivered to the tower from the bottom; water is removed by air from
the top at 26oC. Total heat duty of the tower is calculated (Detailed calculation is shown in
Nawaz, 2013, P17-18)

= 916030.9 415771.5 = 500259/

Ammonium Sulphate Energy Balance

Jason Shek (Shek logbook. (2013-2014) pg. 8-12 for detail energy balance)

The energy balance around the reactor is at steady state. The energy balances are focusing on
heat. Work is neglect for the energy balance. Heat duty is + , where Hrt is
the heat generated in the system (-negative) due to the reaction between sulphuric acid and
ammonia is exothermic.

3.7 The Reactor energy balance for ammonium sulphate crystalliser (reactor):
The reaction to form ammonium sulphate is following:

23 + 2 4 (4 )2 4

17
From the data given in handbook of chemistry and physics - standard thermodynamic
properties of chemical substances, the heat of formation of ammonia, sulphuric acid and
ammonium sulphate are -46.19kJ/mol, -813.989kJ/mol and -1180.9kJ/mol respectively.

The reaction take place at operating temperature would be the following:

= 298 + ..

where Hr,298 is the heat of reaction at 298K, Hf,product is the heat of formation of product and
Hf,reactant is the heat of formation of reactant. The enthalpies which mentioned are in kJ/mol of
ammonium sulphate. Three inlets enter the reactor and two outlets leave the reactor. Stream
enthalpy H can be calculated by using the following equation: = . where is
the mass flow rate of the stream in Kmole/h, Cp is the heat capacity in kJ/kmol and T is the
temperature difference in K. Cp (gas) can be derived as the following (Nist):

, = + + 2 + 3 + 2 =
1000

Where A to E is the heat capacity constants, T is temperature in K.

Ammonia inlet: 33251.18 kJ/h, Sulphuric acid inlet: 2136599.72 kJ/h

Filter recycle: 41569.19 kJ/h, the total stream enthalpy of these three streams: 2211420.05
kJ/h

Stream enthalpy of outlet streams: Two streams exit from the reactor; two enthalpies of
two stream enthalpies are shown below:

Ammonia and water outlet stream enthalpy: 2796.46 kJ/h

Product stream enthalpy: 2921354.10 kJ/h. The total stream enthalpy of outlet streams is
2924150.55 kJ/h.The heat duty is carried out by the following equation: = , +
= . /

3.8 Filter and Sump tank

The following operating units are not included in the heat balance: Filtration unit and sump
tank. As mentioned, heat balance does not included mechanical work. Two units were
assumed there is no heat loss. The changes of stream enthalpies between two operating units
are zero.

18
3.9 Dryer
Detailed calculations for this unit are given on. The heat balance in other operating units has
assumed there is no heat loss. The heat balance around the dryer requires heat. The operating
temperature will assume to be 100oC, which is the boiling point of water. However, this
consideration did not take account of the slurry may act as eutectic mixture, which means it
may not requires the same amount of heat to the slurry to achieve the evaporation of water.
The heat duty of the drying can be carry out by using the following equation:

= , The inlet stream enthalpy is 2872961.62 kJ/h., Outlet stream

(dryer waste) = - 15051.96 kJ/h, Outlet stream (Dried product) = - 6156067.497 kJ/h, the
calculated heat duty by following the equation above, the heat duty would be 3298.16 MJ/h.

Pinch Technology
(For more detail see Jason logbook (2013-14) pg. 80-85)

Pinch Technology
250
Temperature (oC)

200

150

100
Cold stream
50
Hot stream
0
0 10000 20000 30000 40000
Enthalpy (kW)

Figure 2: Pinch Technology for urea and ammonium sulphate plant Pinch
Technology is the development and application to recover the heat between four streams: two
hot streams require cooling, and two cold streams require heating. For the plant between urea
plant and ammonium sulphate plant, 2 reactors are require cooling, Stripper stream outlet and
evaporator outlet are required to heat. From figure2, there is no pinch across the cold stream
so it is more difficult to carry out the recovery of heat. Another factor is the heat load
between the streams is too large; the heat load of ammonium sulphate reactor is much greater
than any other three streams. The pinch technology is possible if the ammonium sulphate
stream is replaced by other which stream requires cooling.

19
 Summary
It was concluded that process one is more suitable than process 2 because the profit made by
process 1 is higher than process2. Capital cost of the process one will be 298Million with a
payback time of 4.6 years but using Taylors method gives payback time of ~2.5years which
proves that Taylor method is more accurate than Short cut method.

4 Individual Design Part

Urea Reactor Chemical Design

4.1 Introduction
The urea reactor is one of the most important units in the urea synthesis process. Liquid NH3
and gaseous CO2 are both fed from the bottom of the reactor generating an upward movement
of the phases with urea product leaves from the top. Urea reactor is considered as gas liquid
co-current reactor in which sieve plates are installed to prevent back mixing. Three different
approaches were made in order to calculate the required volume. Overall reaction rate is a
combination of chemical reaction rate and mass transfer rate where the mass transfer rate is
dominant. Effect of feed ratio on residence time will be carried out along with to find the
optimum operating conditions of the reactor. Sieve plates are used to get the required
conversion of urea product. Thermodynamics and transport aspects along with effect of
temperature/pressure and reactants concentrations on the products will be considered and
finally cooling jacket needs in order to maintain the reactor isothermal conditions.

4.2 Overall mass balance

Table 11: Flow of material across reactor

Input Output

Material Flow rate Flow % Material Flow Molar Flow %

(Kmole/hr.) rate rate rate
(Kg/h) (Kg/h) (Kmole/hr.)
Feed Unreacted
NH3 2846.34 48387 21 NH3 2554 150.26 1.08
CO2 1423.17 62619 27 CO2 3130 71.15 1.30

20
 Product
Recycled 1599.74 124779 52 Ammonium 124779 1599.74 52.93
Ammonium Carbamate
Carbamate
Urea 80167 1336.13 34
H2O 24336 1352.01 0.52
Biuret 818 7.94 0.34
Total 235786 100 Total 235786 100

4.3 Mass transfer Aspects

During the reaction of ammonia with CO2 gas, three factors need to consider. What happened
in the gas and liquid film and in liquid main body? The reaction between CO2 and ammonia is
taken as instantaneous and takes place at the liquid film (Octave, 1999) ) as shown in figure2
which depict the concentration gradient at the gas-liquid interface. The plane of the reaction
spreads into the zone of reaction in which both CO2 and ammonia are present. The absorption
rate of CO2 is high and the reaction itself is fast enough so that this reaction remains totally
into the liquid film and no CO2 enters into the main body of the liquid ammonia.
are the concentration and partial pressure of CO2 at the interface. is partial
pressure of the gas at the inlet and in the concentration of liquid ammonia.

4.4 Reactor Volume

Figure 3: Location of the reaction in the liquid film (Octave, 1999)

4.4.1 1st Approach

(For detail calculations see logbook volume 1 (2013-14) pg.43-47)

Assumptions

Plug flow reactor, No accumulations, Rate of reaction is controlled by mass transfer

Pseudo 1st order reaction (Zahradnik, 1993), Co-current flow
Reactor temperature is 453K and pressure is 14000000Pa

21
 1
= ( ) . . (22)
1 2
+

1
( ) = . (23)
1 2
+

1 = ( )

Calculation:

3 2
2 = 26605 , () = 150 3 , = 3.92 109 / , =

54 105 /

= 2 , where is the concentration of liquid ammonia and can be calculated using

Ideal gas law equation =

= = /, where is the mole fraction of liquid inlet ammonia and is the

reactor operating pressure which is 14000000

= (0.21 14000000) / (8.314 453) = 780.6/3

As we know, = 2 , after putting the values of henrys law constant and ammonia
concentration

= 780.6 26593 = 20767966.82

We now have all calculated variables to put in equation 23 to calculate overall gas transfer
coefficient

Integrated rate equation to calculate the volume of the reactor is given as

2 2
= , = . (24)
1 1 ( )

1 = 2 = 0.27 14000000 = 3780000

2 = 2 = 0.013 14000000 = 182000

22
Where, is the flow rate of gas and is the total pressure of all the components in the
reactor which is 14000000Pa

From mass balance = 395.32/, after putting the values in equation 24

395.33
V=150140000003.92109 2 ( )
= 52.3 2 ( )
1 1

After integrating the equation from 1 to 2 we have

= 52.3 2 ( )
, After integration, = 52.3 [ ]2
1
1

2 1
= 52.3 [(2 ) (1 )] = 52.3 [
] [ ]

2
[]
= 52.3 ln( )
1
[ ]

Plug in the values in equation 6 we have, = .

() = 10.4 = 10.4 (Logbook pg.64)

() = ()

2
= , = 10.4 2 /4 . . (7)
4

We know V= 145.51m3 7

= 2.60 , = 2.60 10.4 = 27

4.4.2 2nd Approach

Volume of the reactor is calculated assuming that the overall reaction rate depends on
chemical reaction and not on mass transfer. Few assumptions has to be made in order to find
the volume

Plug flow reactor, Isothermal reactor

No accumulation/steady state, Ist order reaction

23 + 2 4 2 -84kJ/mol of ammonium carbamate formation

23
4 2 (2 )2 + 2 23kJ/mol of urea formation

First reaction is fast and exothermic but 2nd reaction is slow and endothermic and therefore
2nd reaction acts as slow step and use to find the rate of reaction.

Design equation for plug flow reactor

=
0

Rate of reaction for the reversible reaction is given as

= [ ] + [() ][() ], = ( 1 ), =
( 1 )

= ,

= . (25)
0 [ ] + [() ][() ]

= 0.253 (Detail calculations are in logbook pg.47-63)

4.4.3 3rd Approach

Third approach was used to calculate the volume of the reactor. This approach was based on
the reaction which depends on both rate of chemical reaction and mass transfer. It was
assumed that CO2 is soluble in liquid but ammonia does not enter into the gas. The reaction
can therefore takes place in the liquid phase and at the gas liquid interface. In order to find
the height of the tower, three steps have to follow,

Carry out the material balance over the reactor

Determine the rate controlling step at the top and bottom of the tower, Determine the
height of the tower, Instantaneous reaction

Criteria to find whether the reaction is gas or liquid phase

control if

K g a PA1 > Than the reaction is control by
3

gas phase

24
If

K g a PA1 < than the reaction is controlled by
3

Liquid phase

The reaction was gas phase control at the top of the tower and liquid phase control at the
bottom of the tower. It was then found the point at which the control shift from gas phases to
liquid phase happened. The calculated pressure (P ) where the phase change happened was
200750Pa (see detail calculations in logbook pg. 76-80).

2 1
= . (26)
1 ()

Where rate () which control by both liquid and gas phase

1 2
1
K g +
= +
1 K g a PA 1
3
2 +

= 2.74 109 , = 1.47 1028 3

A comparison was made in order to calculate the volume of the reactor by using an industrial
reactor (Capacity=1500t/d, height=30m, diameter=2m) ( (Dente & Rovaglio, 1992). 1st
approach was based on mass transfer which gave a volume of about 145.5m3. In 2nd approach
it was than assumed that the overall reaction was based on rate of reaction and there is no
mass transfer involved which gave very low volume of0.253. 3rd approach was used by
assuming that rate of reaction is controlled by both mass transfer and chemical reaction. It
was than calculated that liquid film was a controlling factor at the bottom of the reactor and
gas phase was the controlling factor at the top of reactor. It was found that there is a phase
change happened inside the reactor when the pressure reached at 200750pa. However,
calculated length (2.74 109 ) and volume (1.47 1028 3 ). Based on the above
calculations, the best approach was approach 1 which gave a reasonable volume to compare
with the one used in industries.

25
 4.5 Optimum Conditions
In order to find the optimum conditions to operate urea reactor, two graphs were produced as
shown in figure 3 and 4 (see logbook Volume1 (2014) pg.46). Explains how these two
graphs were produced. The pressure and temperature ranges were selected first in order to see
the variation of the reactor volume and rate of mass transfer of carbon dioxide bubbles.
Figure 1.1 shows that the volume of the reactor decreases as the pressure increases. Initially,
it was assumed that the operating pressure of the reactor was 140bar when the calculated
volume was 145.5m3. The pressure of the reactor was fixed to see the variation of reactor
volume. The volume of reactor decreases linearly up to ~82m3as the pressure of the reactor
approaches to 210bar this is because of the fact that the rate of carbon dioxide mass transfer
into ammonia film was increased and therefor required less volume to produced 34% of urea
inside the reactor. Figure 4 explains the behaviour of mass transfer when the temperature
profile is increased inside the reactor. Carbon dioxide bubbles mass transfer rate into liquid
ammonia went up 30 mol/m3.Pa.s from 9 mol/m3.Pa.s between the temperature range of 453K
to 523K. Optimum operating conditions were chosen as 453K and 140bar to in order to
achieve 34% of urea when the assumed carbon dioxide conversion was 95% and the volume
obtained was 145.5m3. As stated earlier, most of the industrial reactor size is around 150m3.
Using approach 1 with an operating condition of 453K and 140bar gave reasonable volume,
height and diameter of the reactor. (Excel file calculations is shown in logbook Volume
1(2013-2014) pg. 46)

Temperatur
Pressure (Pa) Vs. Volume e (K) Temperature Vs. Mass tranfer rate
160 530
520
140
510
120 500
Volume (m3)

100 490
80 480
60 470
40 460
450
20
440
0
0 10 20 30 40
0 10000000 20000000
Mass Transfer Rate (mol/m3.Pa.s)
Pressure (Pa)

Figure 3: Effect of pressure on volume of the reactor

Figure 4: Effect of pressure on volume of

26
4.6 Residence Time
Volumetric flow rate of carbon dioxide was used in order to find the residence time inside the
reactor. Volumetric flow rate of carbon dioxide can be calculated using equation

17.39

() = =
1.9973
= 8.713 / , Residence time is

145.51
given by , / = = 16.71
8.71

Residence time Vs. Feed ratio

5.0
4.0
NH3/CO2 Ratio

3.0
2.0
1.0
0.0
0 5 10 15 20
Residence Time (s)

Figure 5: Effect of ammonia and carbon dioxide feed ration on residence time

Feed ratio of carbon dioxide was first assumed in the range of 2-4 along with the fixed
reactor volume of 145.5m3 to see the variation of residence time inside the reactor (see
appendix 7) shows how the above graph in figure 5 was obtained. The time of carbon dioxide
reaction with ammonia film increased when the feed ratio decreased. The residence time goes
down to 9seconds when the feed ratio of 4 was used. However in my case, no access ratio
was used in previous calculations in order to calculate the mass balance and then the volume
of the reactor just because to reduce the cost and make the process more economical.

4.7 Cooling Jacket

Cooling jacket was used around the reactor in order to maintain the reactor isothermal
conditions. It was assumed that water was feed at 10C and removed at 50 C. The amount of
water needed can be calculate as

From the energy balance, the amount of heat needs to release in order to maintain the reactor
isothermal conditions is given by, = 11293398.1/

Thermodynamics properties of water

27
Table 12: Heat capacity of water2

Cp (kJ/kg.K) T(K) Tref (K)

4.187 323 283
Heat gained by cooling water is given by

= , = = 11293392.1/(4.187 (323 283), = 65858.36/

This is the amount of water needed to maintain the reactor isothermal conditions assuming
that there no phase change occurs inside the reactor.

4.8 Factors effecting urea process

4.8.1 Effect of the reactor outlet temperature on the product yield
2NH3 (l) + CO2 (l) NH4 COONH2 . (27) -84kJ/mol

The reaction is exothermic therefor the value of its equilibrium constant decreases as the
reaction temperature increases.

NH4 COONH2 (NH2 )2 CO + H2 O . . (28) 23kJ/mol

Decomposition of ammonium carbamate into urea and water occurred simultaneously after
first reaction which is endothermic reaction. Consequently, the value of its equilibrium
constant deceases as the temperature increases.

4.8.2 Effect of Pressure

High pressure favoured the overall reaction to move into forward direction. Reactor pressure
is selected according to the temperature and residence time and the pressure is higher than the
dissociation pressure of ammonium carbamate to avoid reversal of reaction shown in
equation 27.

4.8.3 Reactant concentration effect

According to the balance chemical equation, increasing the ammonia or CO2 concentration
theoretically increase the conversion of the CO2 and hence increase the amount of urea in the
product stream. According to the reaction 28, presence of H2O theoretically shifts the
reaction in backward direction therefore, lesser the H2O/NH3 ratio favours for urea
production. However, amount of water needs to be maintains in order to help recycling NH3
and CO2 back to the reactor and to maintain the reactor temperature.

2
NIST online book was used to find the specific heat capacity of water

28
4.9 Sieve Plates (dimensions i.e. sizing)
The principal factor to consider when comparing the performance of sieve and valve plates
and bubble plate are cost, operating range, efficiency and pressure drop. Sieve plates rely on
the flow of vapours through the holes to hold the liquid on the plate and cannot operate at
very low pressure (Richardon, 2009) therefore sieve plates are used in this reactor because
reactor operating conditions are high. The overall height of the column will depend on the
plate spacing. Generally the plate spacing range from 0.5-1m are used and the material of
construction is 304stainless steel. Close spacing are used for small reactor diameter reactor. A
larger spacing will be needed between certain plates to accommodate feed and side stream
arrangement and for men ways. For this reactor

Plate spacing = 1 m, Length of the reactor = 27m, Total number of plates or stages required =
27/1 = 27

Conclusion
It was concluded that the optimum operating conditions are 140bar and 180C which are well
in the range of current industrial reactors, residence time was found to be 16.71seconds. 27
sieve plates needed for 95% conversion of CO2 gas to get 34% of urea product by using plug
flow isothermal reactor. Volume of the reactor is 145.5m3 with length of 27m and diameter is
2.61m.

5 Mechanical Design

5.1 Introduction
Detail mechanical design of urea reactor will be carried out in order to find the reactor wall
thickness, reactor insulations and materials of construction. Skirts are used for reactor support
and detail calculations for the skirt thickness will be carried out. Stress analysis and dead
weight of the vessel helped to find the whether the reactor is able to withstand the current
load on it. Two inlet streams and two recycled streams coming to the reactor with one outlet
stream are considered to find the diameter of the pipes, flanges calculations and pressure drop
across each line. Finally half pipe cooling jacket is needed to maintain the reactor
isothermal condition and to find the heat transfer coefficient of outside wall of the reactor.

29
5.2 Classifications of pressure vessel
For design analysis purposes, pressure vessel such as urea reactor classified as thin wall or
thick wall depending on the ratio of wall thickness to vessel diameter. If the ratio is <1:10
than vessel is considered as thin wall but vessel will be considered as thick wall if the ratio is
higher than 1:10 (Sinnott & Towler, 2009). Based on the calculated reactor diameter shown
in chemical design part which is 2.6m and the reactor wall thickness 0.103m (wall thickness
calculation will be shown in the following section).

Wall thickness 0.103m

= = 0.0396
vessel diameter 2.6m

According to the calculated ratio, it can be seen that the pressure vessel is classified as thin
wall.

5.3 Pressure vessel codes and standards

Design and construction of reactors or pressure vessels is covered by national codes and
standards and the purpose of this is to establish rules of safety relating to the design and to
provide guidance on material of construction, inspection and testing. The ASME Boiler and
Pressure Vessel (BPV) Code Divison1 standard is used (logbook Volume 1 (2013-14) pg.
982for more detail).

5.4 Reactor vessel design consideration

5.5 Material of construction

Carbon steel alloy is used for urea reactor wall because it is durable and cost effective during
high pressure operation for example in case of urea reactor where operating conditions are
high (150bar and 180C). Coefficient of thermal expansion of this alloy is low (1.2
mm/m/100oC) compare to other metals like steel (1.2 mm/m/100oC) making it perfect to use
in industries (Brouwer, 2009). The function of carbon steel wall is to resist high
pressure/temperature at which the process operate.

Ammonium carbamate which produces during the formation of urea inside the reactor is very
corrosive material and there are high chances of corrosion which can affect the urea product
rate and carbon steel performance. To protect this happening, a protective layer or liner is
used inside the reactor and the material of liner can be 316L Urea Grade, 25-22-2 stainless
steel, titanium or duplex. The thickness of the liner varies between 4 and 10 mm (Brouwer,

30
2009). Liner thickness of 10mm will be used for calculation because of the high operating
conditions of the pressure vessel and due to the high corrosiveness of ammonium carbamate.

Titanium has been widely used in urea synthesis process due to its good passivation and
corrosive resistance properties. The life time of titanium is limited. Stainless steel on the
other hand is almost immune to erosion and has good weld ability but required large amount
of passivation air compare to titanium (Juneja, 2013). 316L Urea Grad is used for long time
in urea synthesis reactor due to its low cost and fair corrosive resistance properties but due to
large amount of passivation requirements, its operability is restricted. Duplex shows excellent
corrosive resistance. It possesses better resistance to stress, corrosion cracking. Comparison
has been made to select the right liner with right properties, based on the table 13and the
decision analysis table (see appendix 2), duplex stain less steel is chosen as a protective layer
(liner)

Table 13: shows the advantages and disadvantages of different materials of constructions.

S.no Insulations Advantages Disadvantages

1 Stainless Steel 1. Good weld ability 1. Large amount of

2. Good to resistance passivation air

2 Titanium 1. Reasonable 1. Difficult to weld

passivation properties 2. Costly
for less air3
2. Good corrosive
resistance
3 Duplex Stainless 1. Good weld 1. Lower ductility
Steel ability/toughness
2. Good corrosion
resistance
3. Double the strength
compared to austenitic
stainless steels less

3
Passivation refer to material becoming passive means less effective due to environmental factors such as air
or water

31
 stress corrosion
cracking (SCC)4
4 316L-Urea Grade 1. Large amount of 1. Large amount of
passivation air passivation air

5.6 Reactor operating conditions

Table 2.2 shows the reactor operating conditions. Normally 10% of the reactor operating
pressure will be used to avoid spurious operation of the pressure relieve valve during minor
operation upsets or breakdown (Sinnott &Towler, 2009). Operating pressure will be

0.10 14000000 = 15400000Pa

Table 14: Design operating conditions and material of constructions

Design Pressure 140bar=14000000Pa Material for lining Duplex stain less

steel

Design Temperature 180C = 453K Liner thickness 10mm

Maximum allowable 100% Corrosion 2mm

joint efficiency(see allowance (see
logbook pg.115 logbook pg.116)

Material of construction Carbon steel Maximum 105 106 N/m2

for reactor vessel allowable design
stress (see logbook
pg.115)

5.7 Reactor vessel load calculations

Major load on reactor will be

1. Maximum weight of reactor and its contents (sieve plates)under operating conditions
and hydraulic test conditions
2. Deign pressure including ant static head of liquid
3. Wind load and load due to eccentric equipment (cooling jacket)

4
SSC is a form of corrosion which occurs during tensile stress, corrosive environment and at higher
temperature and pressure.

32
5.8 Reactor wall thickness calculations
The shape of the urea reactor is cylindrical and thickness required to resist the internal
pressure of the vessel can be calculated using given formula

= 41.2, P=internal pressure = 15400000Pa, J= joint efficiency = 100%, D=vessel

diameter = 2.6m, f= maximum design stress = 105 106 N/m2

After inserting all the variables into the above formula, = 0.100

After adding 2mm for corrosion allowance the total thickness of the reactor will be, =
0.102 (detail calculations is in logbook pg116)

Although minimum practical wall thickness is 10mm for reactor having diameter range
between 2.5-3m (Sinnott & Towler, 2009, p. 1004). In this case, the required thickness is
0.100m. This is because the reactor is operating at higher temperature and pressure. Normally
wall thickness used for urea reactor manufacturing is in between 100-300mm (Brouwer,
2009, p. 3) which proves that the reactor calculated wall thickness is in the range of currently
working industrial reactors.

5.9 Heads and closures

Please see logbook Volume 1(2013-14) pg.117 for more detail calculations.

5.9.1 Hemispherical head thickness calculations

Hemispherical, torispherical and ellipsoidal heads are normally used as end closures for
vessel. Torispherical and ellipsoidal heads are used where less pressure is required normally
in the range of 15 bars but hemispherical head is the strongest head used for vessel having
large pressure. The material of construction of head will be the same as reactor (carbon steel)
to avoid from thermal expansion and dilation between the head and reactor. In the ASME
BPV Code Sec. VIII D.1 the equation specified to calculate thickness of the hemispherical

head is , = 40.4, Where P is the design pressure, S is maximum allowable design stress,

D is the diameter and E is the joint efficiency. After plugging in the values, the thickness will
be, = 0.094 = 94

5.9.2 Diameter/length calculations

The diameter of the head will be the same as the diameter of the reactor because it is
hemispherical head and the whole purpose of this is to
cover the reactor head. Head length (see diagram 2.2)

33
will be the half of the diameter size and corrosion allowance will be the same as reactor
(2mm).

5.10 Combine loading

The reactor is subjected to other loads in addition to the pressure for example, dead weight of
the vessel, wind, earthquake and external loads imposed by the vessel. Compressive and
tensile stress must be considered during combined load analysis. Primary stresses arising
from these loads are considered in the following stress analysis section.

5.11 Stress analysis

5.11.1 Longitudinal Stress

Longitudinal and circumferential stresses due to internal pressure vessel given by,

PD
=
2t

Where P is design pressure, D is internal diameter; t is the reactor wall thickness

= 1.95 108 /2 (See logbook pg.118 for more detail calculations)

5.11.2 Circumferential stress

PD
Circumferential stress will be calculated as, = 4t

After plugging the values, = 9.75 107 /2 (See logbook pg.118 for more detail
calculations)

5.11.3 Direct or dead weight stress

Direct stress due to vessel weight, its contents and any attachments, stress will be tensile
(positive) for the points below the vessel support and compressive (negative) for the point


above the vessel support. Direct stress can be calculated as, = (+)

Where = 2444930 is the total weight supported by the

reactor wall at the plan and t is the reactor thickness, D is the

34
reactor diameter. Direct stress is considered as compressive (negative) stress and therefore
acts on the points above the vessel support.

Figure 6: stresses due to dead weight load

= 2.82 106 / 2 (See detail
calculations in logbook pg.119)

5.11.4 Bending stress

Bending stress resulting from the bending moment to which reactor is subjected for example,
wind load, dead weight of the vessel and its contents and wind loads on piping and equipment
that is attached to it. Bending stress can be positive (tensile) or negative (compressive)
depending on the location can be given by the formula

= ( 2 + ), = 64 (4 4 )

Where M is total bending moment at the plan and is the second moment of area about the
plan of bending. is the outside diameter of the reactor vessel. can be calculated from

the reactor thickness using the formula, = 2

2
= Where, = = 3630.08/, = =
2

27, = 1323164.16 Nm , = 0.812 , = 2.816

= 2.6, After plugging the value into the above formulas, = 2.30 106 /2

5.11.5 Total longitudinal stress

= + , = (9.75 107 ) 2.82 106 2.30 106

is compressive and therefore negative

Upwind = (9.75 107 ) 2.82 106 + 2.30 106 = 9.69 107 /2

Downwind=(9.75 107 ) 2.82 106 2.30 106 = 9.24 107 /2

35
There is no torsional stress and principal stresses are 2 = and1 = (see logbook pg.
122-123)

Figure 7: Stresses in cylinder under combine loading

From the above figure the maximum difference in principal stress are in downwind side
which is 1.02 107 /2 which is below than the maximum allowable design stress
(1.05 108 /2 ) which prove that the current stress analysis is right.

5.12 Dead weight of vessel

The major source of dead weight loads are

1) Reactor vessel
2) Reactor fittings i.e. man ways, nozzles, Internal fittings (sieve plates), Auxiliary
equipment (Cooling Jacket)
3) Insulation, Liquid weight inside the pressure for hydraulic pressure test

Assuming that the reactor wall thickness is uniform, the dead weight of the reactor can be
calculated from the equation given below

= 240 ( + 0.8 )

= Reactor total weight excluding internal plates, N

= 1.15 A factor to account for nozzle weight, man way, internal support, = Mean
diameter of vessel = ( + 103 ), , = Height of the reactor, m, t= wall
thickness, mm, = 2249587 = 2249.587 (See detail calculations in logbook pg.
124)

5.12.1 Weight of the plates

2
= 2 = Where d is reactor diameter which is 2.6 m
4

36
 = 5.352, Weight of the plat including liquid on it, 1.2 5.35 = 6.24 (See
detail calculations in logbook pg. 125)

Total numbers of plates are 27 so total weights, 27 6.24 = 173.34

5.12.2 Insulation weight

Mineral wool insulation is used because of it can be applied very easily and have good
thermal conductivities range from 0.07 W/mK to 0.21 W/mK (L.Fiala, 2006) depending on
the operating conditions., Insulation thickness= 38.1 mm ( Perry, 1997), Density of material
= 130kg/m3, Allow to double the density for attachment fittings and sealing (Sinnott &
Towler, 2009)

= 3.14 27 2.6 0.0381 = 8.433 , = / , =

8.43 2 130 9.81 = 21503.1 = 21.503

5.12.3 Total weight

Table 15: total weight of vessel

Weight of vessel 2249.59kN

Weight of plates 173.34kN

Weight of insulation 21.50kN

Total Weight 2444.93kN

5.12.4 Dynamic wind pressure

A wind speed of 100mph can be used to estimate for design purpose which is equivalent to
the dynamic wind pressure of 1280N/m2 (Sinnot & Towler, 2009, p. 1025)

5.13 Vessel support

The method used to support vessel depends on size, weight, design temperature and pressure.
Skirts are normally used for tall vertical column subjected to wind load. Skirt thickness must
be sufficient to withstand the design load. Skirt support consists of cylindrical shell welded to
the base of reactor. Opening must be provided in skirt for any connecting pipe for example,

37
for ammonia, carbon dioxide and ammonium carbamate inlets. Material of construction of
skirt is carbon steel which is same as reactor wall material.

5.14 Skirt thickness

(Detail calculations are given in logbookVolume1 (2013-2014) pg.126-146)

The skirt thickness must be sufficient to withstand reactor load and bending moment imposed
on it. Typical skirt design and preferred skirt support is given in figure 8.

Figure 8: skirt support and skirt support design

For straight cylindrical skirt the base angle is = 90

Maximum allowable design stress ( ) normally taken at ambient temperature =

=200000106
135 106 /2 at (0 50), Young modulus of carbon steel , Maximum dead
2

weight of vessel on skirt will occur when the vessel will be in full of fluid

Approximate weight of fluid= 1416.4kN, Weight of pressure vessel= 2444.43kN, Total

weight = 3860.83kN

Wind load per linear meter = 3.63kN/m, Bending moment at the skirt base is given by
formula

2
= Where w is wind load per linear meter and x is total height of cylinder including
2

hemispherical heads height on both ends and skirt length. = 1930.09, Resultant
stress in the skirt can be calculated from tensile and compressive stresses as follow

() = , () = +

4
Where the bending stress in the skirt and is can be calculated as, = (+
)

38
 Is the dead weight stress in skirt and can be calculated using the formula, =

(+ )

is skirt thickness and is inside diameter of reactor which is 2.61m,

=Total vessel weight and its contents, = Bending moment at skirt which is
1903.09kNm

NOTE: Skirt thickness was assumed to be 95mm in order to check whether this thickness
can withstand dead weight stress ( ) under operating and test (when the vessel is full of
water) conditions.

106
= 8.56 , () = 4.79 106 /2 , () = 3.03 106 /2
2

In order to fulfil the design criteria the following conditions has to be followed in worst
combination of wind and dead weight

1. () < s

2. () < 0.125 s

Where is maximum stress (135 106 /2 at (0 50))

= 90, =
0.85, () = +
107
(), () = 1.348 2
, () =
(), () = 5.35 106 /2

From the above design criteria,

1. 5.35 106 /2 < 1.15 108 /2

2. 1.35 107 /2 < 9.09 108 /2

Both conditions are fulfilled for skirt thickness

Total skirt thickness including 2mm of corrosion will be = 95 + 2 = 97 = 0.097

6 Eccentric load

39
6.1 Cooling jacket
There are different cooling jackets are available in the market depending the operating
conditions. However in order to find the right jacket, several factors need to be considered,
for example, cost, heat transfer rate required and pressure as a rough guide. Half pipe cooling
jacket can withstand pressure up to 70bar (Sinnot & Towler, 2009, pp. 956-957) and less
pressure drop than other jackets. In order to fulfil the design operating conditions (140bar and
453K), half pipe cooling jacket can be used as it can withstand high pressure. Standard sizes
of the half pipe jacket are 2 3/8, 3 and 4 -in.o.d. Thickness can be used as 3/16-in. for 2
3/8-in.od. and in for both 3 and 4 1/2 in.od (McKetta, 1992, pp. 423-424) however
cooling jacket diameter and thickness can be slightly varied in order to accommodate the
higher pressure and temperature conditions and will be shown in the below calculations. Half
pipe cooling jacket is normally fabricated by 304stainless steel to avoid problem like
differential thermal expansion. Standard Heat transfer coefficient at outer wall of reactor and
pressure drop through the half pipe cooling jacket is calculated as follow,

6.2 Heat transfer coefficient (hi) at reactor outer wall

(See logbook1, pg. 82-90 for detail calculations)

= 120,, =
10, = 100

Water is used as a coolant with an inlet temperature of 10C and outer temperature of 50C in
order to maintain the reactor isothermal conditions.

Water mass flow needed to maintain the reactor temperature = 65858.36Kg/h

It was assumed that the space between jacket and reactor wall is 300mm and jacket is
extended up to 15m

= 100, Equation to use in order to calculate the heat transfer

coefficient

= 0.8 0.33 (/ )0.14

Water is not a viscous so viscosity of water can be neglected in the above equation

0.8 0.33
= ( ) . (29)

40
Where is Reynolds number and is Prandtl number and can be calculated using formula

= ( /) , = /Kf, = 288698.27 > 4000 so by definition

water will be in turbulent region if Reynolds number is greater than 4000

5
Table 16: physical properties of water and other dimension less parameter

( ) 0.096 Cp of water 75.06J/K.mol

( ) 287437.27 Viscosity of water () 0.000796

Pa.s

Fluid velocity 2.29 m/s Frictional factor (Jf) 2.5 103

Hydraulic diameter (dh) 0.1m C 0.023

Thermal conductivity of fluid (Kf) 0.622W/m.K Water mean 30 C

temperature

Length of one tube 5.42m Length of total tubes 135.5m

Space between cooling jacket and 300mm Material for cooling Carbon steel
reactor jacket

(fluid viscosity at wall) 0.00090Pa.s Pressure 50bar

The heat transfer coefficient can be calculated using equation (29)

= 1536.69/2 .

5
Specific heat capacity, thermal conductivity and viscosity of water is obtained from NIST hand book at mean
temperature of 30degree

41
 Heat Tranfer Coeffecient Vs. Velocity of coolant
2.5

2
Velocity (m/s)

1.5

0.5

0
0 500 1000 1500 2000

Heat Tranfer Coeffecient (W/m2.K)

Figure 9: Heat transfer coefficient from the reactor outer wall with respect to coolant velocity

Graph shown in figure 9 is produced from equation 29 by varying the velocity to see the
effect of heat transfer coefficient (hi) at the reactor outer wall. The graphs shows that the
transfer coefficient is increased linearly by increasing the velocity of the coming fluid though
the cooling medium from 0.76 to 2.30m/s. Typical velocity ranges given in the literature is
0.76-1.6m/s (McKetta, 1992, pp. 418-420). Normally the selection of heat transfer
coefficient is based on lowest possible velocity 0.76m/s for heat transfer coefficient of 635
/2 . but the in my case, the velocity is 2.29m/s which gave heat transfer coefficient
of 1536.69/2 . , this is because more coolant flow rate enters in the cooling jacket and
required more heat transfer in order to maintain the reactor isothermal conditions.

6.3 Pressure drop across tube ()

Detail calculations can be found from, logbook 1, pg.88-90)

There are two major sources of pressure losses inside the tube, 1st is pressure drop due to
friction and 2nd is pressure loss due to sudden contraction and expansion. The equation to use
in order to find the pressure drop when the flow is not isothermal,

2
= 8(/) ( )
2

is the viscosity of fluid at the tube wall and it was calculated by assuming that the bulk
temperature is 30degree and the temperature at the wall will be bit lower than the bulk

42
because of heat transfer it as assumed to be 25dgree and the value of viscosity at this
temperature will be 0.00090Pa.s using NIST data book.

After plugging all the values given in table above the pressure drop in the tubes can be
calculated, = 3634.02/2. Pressure drop across the tubes can be optimized by the
variation of the fluid velocity. Lowering the fluid velocity will results in lowering the
pressure drop

7 Pipe Sizing and pressure drop

(Detail calculations for pipe sizing and pressured drop is given in logbook1, pg. 147-158)

Four inlet streams and one outlet stream need to find the diameter of the pipes. One is
gaseous carbon dioxide, 2nd is ammonia and 3rd is ammonium carbamate recycled stream and
4th is (NH3+CO2) recycled stream and one outlet stream for urea production. 304 Stainless
steel materials are used for pipe construction because of its long durability and low corrosion
properties. Capital cost of pipe run increases by increasing in diameter but pumping cost
decreases in increasing pipe diameter. Different methods are available in the literature to
calculate the pipe diameter however the simple way to calculate the pipe diameter is given in
Richardson and Coulson edition 5, pg.265. Pipe diameter of each of the pipeline is calculated
using formula = where A is the cross sectional area in m2 of the pipe and V is the
velocity in m/s and q is the volumetric flow rate in m3/s. where pressure drop is calculated

using equation = 8 () v 2 /2, where = density of the fluid, L and d are the length

and diameter of the pipes, v is the velocity and f is the frictional factor.

Table 17: Typical velocities and allowable pressure drop (Sinnott & Towler, 2009, p. 259)

Velocity(m/s)
( )

Liquid, pump (not viscous) 1-3 0.5

Liquid, gravity flow - 0.05

Gases and vapours 15-30 0.02%of line pressure

Table17a: Pipe diameters and pressure drop in the pipe lines

43
 CO2 gas pipe NH3 pipe Ammonium (NH3+CO2)
Carbamate recycle recycled stream
stream pipe pipe

Diameter (m) 0.601 0.138 0.097 0.05

Pressure 23.606 128.97 10

Drop(KPa)

8 Flanges
Flanges are cast ring of carbon steel designed to join pipe to a pressure vessels like reactor to
give extra strength to pipe. Several types of flanges are available for different applications
like welding-neck flanges, slip on, lap joint flanges and screwed flanges. Typical flanges are
shown in figure 8a.

Figure8a: Flange types: (a) welding neck, (b) slip-on (c) Lap-joint (d) Screwed with
dimension of welding neck flange

Welding-neck flanges have long tapered hub between the flange ring and the welded joint. These are
suitable for extreme service conditions where the flanges are most likely to be subjected to
temperature, shear and vibration load and therefore it is the ideal for urea reactor. Four flanges are
needed for urea reactor, two for NH3 and CO2 and two for carbamate and (NH3+CO2) recycled
streams. Typical dimensions given in ASME B16.5 standards for pipe flanges and flanged fittings are
given in table 8a.

Table 15a: dimensions of flanges used for different pipes

44
Pipe lines Nominal size Outside Thickness Raised faced Fillet radius
(inches) diameter (o) diameter (R)
(c) (inches) (r) (inches)
(inches) (inches)

CO2 24.01 32 1.88 27.27 0.50

NH3 5.44 11 1 8.50 0.50

Carbamate 3.82 8.50 0.94 5.50 0.38

NH3+ CO2 1.97 6 0.75 3.62 0.31

Conclusion
Reactor wall thickness of 100mm was found enough to support the reactor operating
conditions. Material of construction for reactor and its heads are carbon steel. Minimum
corrosion allowance of 2mm is used for the reactor because of ammonium carmabate which
found to be really corrosive material. Suitable material for insulation was found to be mineral
wool. Combine weight of the vessel is 2444.93kN which found reasonable for stress analysis.
Hemispherical heads are used for top and bottom ends because of its high demand for higher
pressure vessels. Cooling jacket water flow of 65858.36Kg/h is needed to maintain the
reactor isothermal conditions.

9 Engineering Design

45
 Figure 8b: Reactor dimensions

10 Design Specifications
Design specifications sheets for mechanical design and vessel design are attached in the
appendix 9. However, due to poor scanner quality, specification sheets are also attached in
logbook Volume 2, (2014) pg.40.

11 Costing
(Detail calculations can been seen in logbook2, pg. 19-39)

11.1 Introduction
Factorial method is used to calculate the cost of reactor and its attachments using installation
factor called Lang factor. Cost of pumps, compressors, cooling jacket and sieve plates will
be calculated to find the total cost of the reactor and finally location factor and M&S Cost
indices will allow finding the cost in UK in 2010.

46
11.2 Factorial method of cost estimation
Capital cost of reactor is often based on the purchased equipments cost of the main process
and other cost can be estimated as a factor of the equipment cost. Accurate estimation of the
plant capital cost can be made by using Land Factors using the formula (Sinnot & Towler,
2009, pp. 306-320)

= . . (31)

= Total delivered cost of all the process equipment items: reactors, pumps, compressors,
etc. This can be calculated using the formula

= + () . . (32)

= Installation factor known as Lang factor, = Total Plant Inside Battery Limits (ISBL)
cost which include all the procurement and installation cost of the plant, , =
( 2, . 20 21)

S=size parameters, = 3.1 for solids processing units, = 4.74 for fluid processing units,
= 3.63 Mixing fluids-solids processes units

However Hand (1958) suggested that using different factors for different types of equipments
will give more accurate results as shown in table 18 below. Therefore the costs of each of the
equipments will be based on the factors and the total cost will be in US$ in 2007.

The formula given in equation 32 will be used in order to calculate the cost of each of the
equipments and once the cost is calculated, it needs to multiply by the material cost factors
() relative to the plain carbon steel to fins the total cost of the equipment. For example,
sieve plates are constructed by 304stainless steel, so once the cost of the sieve plates is
calculated, it needs to multiply by cost factor of 1.3 (see table 18)to get the total cost of the
sieve plates.

Table 18: Materials cost factors (fm) relative to the plain carbon steel. Installation factor proposed by Hand

Materials Equipment Type Installation Factor

(F)

47
Carbon Steel 1 Compressors 2.5

Aluminium and 1.07 Distillation Column 4

bronze

Cast Steel 1.1 Fired Heaters 2

304 stainless steel 1.3 Heat Exchangers 3.5

316 stainless steel 1.3 Instruments 4

321 stainless steel 1.5 Pressure Vessel 2.5

Monel 1.65 Pumps 4

11.3 Major equipments items

Reactor, Sieve plates, Two pumps were used for NH3 inlet stream (one is used as backup),
Two pumps were used for ammonium carbmate recycled stream (one is used as backup),
Two pumps were used for cooling jacket (one is used as backup), Two pumps were used for
(NH3+CO2) recycled stream coming from decomposers to urea reactor (one is used as
backup), Centrifugal compressor for CO2 stream.

Table 19: purchased equipment cost for common plant equipments

Equipment Units for Material of a b n ($) Cost (C)$

size (S) constructio
n

Jacketed, 145.51m3 304 53000 2800 0.8 1557777.56

agitated stainless 0
reactor steel

Pressure 229315.69k Carbon 10000 29 0.8 1054159.16 4216636.6

Vessel g steel 5

27 Sieve 4.63m 304 110 380 1.8 16164599.1 213978.93

plates stainless 8
steel

48
Two 18.15L/s 304 6900 206 0.9 19396.1 100859.7
Pumps for stainless
cooling steel
jacket

CO2 2704.66kW 304 49000 1680 0.6 2.4 106 7800000

Compresso stainless 0 0
r steel

Two NH3 43L/s 304 6900 206 0.9 25962.39 135004.4

Pumps stainless
steel

Two 23.64L/s 304 6900 206 0.9 20898.17 108670.5

Ammoniu stainless
m steel
Carbamate
recycled
Pumps

Two 6.77L/s 304 6900 206 0.9 8051.85 83739.2

(NH3+CO2 stainless
) recycled steel
Pumps

Total cost 12658889.

3

Table 19 shows the cost of individual equipments. Following the Hands rule given in
equation31, the total cost of individual equipments can be calculated by multiplying with
relevant installation factor (F) and materials cost factors (fm) as shown in table 18. The cost
of the reactor was calculated using two different approaches, firstly it was assumed that the
reactor is acting as agitated jacketed vessel but it gave higher cost (1557777.56$) than
assuming pressure vessel (1054159.16$). Same procedure applied in calculating the cost of
pumps, compressors and sieve plats. The compressor power was calculated using formula,

49
 1
1000
= 243600 ( )( )[ 1] ( McCollum, 2006)
1

62619
= , = 2 = 44/, =

8.314
75%, = 70.5, = . , = ( ) =Average ration of specific heat of carbon

dioxide, = Average carbon dioxide compressibility

The values of and at 140bar obtained by plotting graph using Excel sheet (See
logbook2, pg.30 for more detail calculations). From graphs Ks=1.47, Zs= 0.72

= 2704.66kW

1.5
1.2
1.45
1
1.4
Ks 0.8
Series1
1.35 Series1
Zs 0.6
1.3 Linear 0.4
(Series1) Linear
1.25 0.2
0 5 10 15 (Series
0 1)
Pressure (MPa) 0 5 10 15
Pressure (MPa)

Figure 10: Specific heat (Ks) of CO2 Vs. pressure Figure 11: CO2 compressibility (Zs) vs. pressure

The total ISBL cost of the plant is given in table 19 which is 12658889.3$

The cost of the urea reactor is very high and this is because of the compressor cost which is
7800000$. The centrifugal compressor cost itself covers about 62% of the total urea reactor
cost. In order to reduce the cost, it was decided to use reciprocating compressor and then use
given in table 6.6 (logbook, V2, pg.20) which gives a cost of million 3.5$ (logbook V2,
(2013) pg.36. Using reciprocating compressor, the total cost of the reactor will be
8377357.9$ in 2007

11.4 Scale up Method

M&S cost indices in year 2007 and 2014 will be needed in order to scale up the plant to find
cost in 2010,

Cost index in 2003 = 1123.6 (Sinnott & Towler, 2009, pp. 318-20)
50
Cost index in 2007= 1373.3 (Sinnott & Towler, 2009, p. 31820), Using extrapolation from
period 2003 to 2007 M&S cost index will be 1560, (2010) = 8377357.9
1560
(1373.3) = 9516258.8$, Location factor for UK relative to a USGC installation= 1.02

(Sinnott & Towler, 2009, p. 320), Exchange rate in December 2003= 1=1.76$, Exchange
1.55
rate in 2010= 1=1.55$ (converter, 2014), Location factor for UK in 2010 = (1.76) 1.02 =

0.89, Cost of building urea plant in UK in US$ in 2010 =0.89 8377357.9 = 7525342.5$ ,
7525342.5
Cost of building urea plant in UK in in 2010 = = 4855059.7
1.55

Conclusion
The cost of whole plant was found to be 12658889.3$ which seems bit high because the cost
of CO2 centrifugal compressor itself covers 62% of the whole cost but using reciprocating
compressor reduce the cost to 8377357.9$. The cost of the plant based on 8377357.9$ in UK
in 2010 will be4855059.7.

12 Heath Safety and Environment (HSE)

12.1 Safety
The safe design and operation of the facility is very important to every company that is
involved in manufacturing of fuel, fertilizers, chemicals and pharmaceuticals. Due to the
particular hazards associated with processing of large quantities of hazardous materials, most
of the countries enacted legislations in order to ensure that the best safety practised is
followed. In UK, Health and Safety at Work etc. Act (1974) (HSW) set legal rules and
requirements for their workers, employees and general public and force them to follow the set
rules (Sinnott & Towler, 2009, pp. 474-475). Flammability like flash point (measure of ease
of ignition of a liquid), auto-ignition temperature (the temperature at which the material will
ignite spontaneously from air) and flammability limits are the lowest and highest
concentration of the materials in air at standard temperature and pressure.

Table 20: Flammability, hazards identification, and PPE for NH3, CO2 and Urea and carbamate

Ammonia

Flammabilit Reactivit Hazards Emergen Fire Handling PPE

y and y and identificati cy Extinguis and

51
toxicity stability on procedur her storage
e

Slightly Lower Corrosive Flush Extinguish Store in Gas tight

flammable. stability and eyes with er media cool, dry chemical
and irritating if copious are water and well- goggles,
Flashpoint:
converts exposed to quantities fog, foam ventilated safety shoes
N/A
into skin. of water and use area and and
Flammability NH4OH Harmful if for water use protective
: N/A by inhaled. 15minute spray for pressure gloves. Air
reacting Will cause s and surroundin indicator purifying
Auto-
with H2O. swelling of person g when respirators
ignition
No eyes if with containers. connectin should
Temperature:
reactivity contacted. potential g equip with
1274oF
under Exposure exposer cylinders suitable
normal of 50ppm to NH3 to lower cartridges.
condition for 5 should pressure
s minutes not wear (less than
was not contact 500psi)
considered lenses. piping
irritating Seek systems.
but more medical Do not
than attention exceed the
700ppm if temperatur
cause ingested e from
severely or 52degree
irritating. inhaled. where
cylinder is
stored.

Ammonium
Carbamate

Not Moisture Very Wash Fire Stored Gas tight

flammable. It sensitive corrosive immediat extinguish outside splash

52
can be and stable material ely with er media is non- goggles,
explode on compoun and severe water for water. combustib chemical
contact with d. It eye 20minute le resistant suit
ignition decompos irritation s if location. with vinyl
source if es into will occur contacted Otherwise gloves and
there are NH3 and at NH3 with eyes store in rubber
ammonia CO2 con. Of and skin dry, cool boots. Use
vapors in the when 100PPM. and seek and well- NIOSH/MS
range of 16% heated 1st 2nd and medical ventilated HA
to 25%. above 3rd degree assistance area and approved
140 burn when . away from full face ve
Flash point:
degree. contacted all pressure
N/A
Reacts with skin. ignition respirator
Flammability with Ingestion sources fitted with
: N/A chlorine, could and NH3
hypochlor cause oxidizers. cartridges.
Auto-
ite to death.
ignition
form Coughing
temperature :
explosive and
N/A
compoun bronchial
ds. spasms
occur if
inhale.

Biuret

Combustible Stable Acute Wash Use water Keep Safety

but not under health skin and spray, away from glasses, dust
flammable at normal effect: eyes with foam or ignition respirator,
STP. condition irritant in water and fog. source and splash
s and case of cover the heat and goggles in
Auto ignition
does not skin irritated avoid case of large
temperature:
change contact or skin with contact spill. Self-
N/A
with eye emollient with skin breathing

53
Flash point: temperatu contact. No and seek and keep apparatus
N/A re carcinogen medical container used to
ic, advise close avoid
Flammable
mutagenic tightly and inhalation.
limits : N/A
effect. place
under
well-
ventilated
area.

Urea

Urea is non- Produced According Wash CO2, Store in Suitable

flammable. biuret to HS affected water acts cool dry mask
Flash point: when (2001) areas with as fire and well- needed if
N/A heated. (minimum soap and extinguish ventilated dust
Should degree of water and er area. particles are
Auto-
store hazards), it get Wash present.
ignition
under dry is harmful medical hand Safety
temperature
condition if assistance thoroughl glasses and
:N/A
s because swallowed . In case y after gloves.
Flammability of its high or inhaled of using it.
/A. urea solubility and cause ingestion, Avoid
produces and high eye induce unintende
toxic gases stability irritation. vomiting d release
like CO2 at STP. after to the
which carries giving environme
fire and glass of nt.
explosion water.
hazards.

12.2 HAZOP and P&ID

Hazards and operability studies (HAZOP) is a technique for the examination of the
operability of a process. When used in conjunction with a process plant it can indicate

54
hazards that arise from deviations from usual design conditions and procedure. Each study is
carried out focusing on one area of a P&ID diagram called a node, guidewords and
parameters are used to specify the area under inspection. Meaningful deviations are then used
to illustrate potential hazards to safety, health or the environment. The HAZOP is done only
on meaningful deviations, which can be physically possible, i.e. no flow, high temperature
or high pressure. One of the examples of HAZOP is carried out on deviation called high
pressure in urea reactor and the cause of it is the blockage in the urea outlet pipeline which
can cause rupture as consequences, to protect this from happening, a pressure relief valve is
used as a safeguard. Detailed analysis of the HAZOP is shown in the table given in appendix
8.For this report the HAZOP has been completed for the urea reactor, its streams and its
cooling jacket Once this had been completed the additions to the P&ID were made, this
included adding

Level alarms on all storage tanks, temperature indicator on the reactor

Flow meters and controllers on all inlet streams, temperature indicators on the outlet
stream
Pressure indicators and valves on the reactor and ammonia inlet stream

12.3 Process control and Instrumentation Diagram

The P&ID diagram was initially completed to ensure that the system worked correctly
without taking into account the health and safety aspect of the unit. Once a working model
was established, the P&ID was altered to include the HAZOPs recommendations. The
methods used to design the P&ID guarantees that the unit works correctly, the working
conditions used are appropriate, and most importantly if a malfunction occurs, the correct
safety procedures are in place to minimise the damage. The alterations that were made to the
P&ID diagram after the HAZOP had been completed see figure 12. See appendix7 for colour
coded P&ID.

55
 Figure 12: P&ID for urea reactor after HAZOP

Once the HAZOP had been completed, the equipment was added to the original design which
included temperature, pressure, flow controllers and back-up pumps and compressor.

Control process

Controller of any processes can be defined as a several tasks which will ensure the stability
and controllability at the level of performance with only normal variation. Process control is
applied to different unit operations to enable production of desired product at specific
temperature and pressure without facing hazardous cases. The controllers of studied reactor
are:

1) Pressure Process:

Pressure controllers are used to control the pressure inside the urea reactor. As in case of
cooling water out shown in figure 12, if the pressure inside the urea reactor exceed the limits
of set point than pressure indicator will send the signal to the pressure indicator controller
shown in blue arrow to open the control valve and ultimately to control and maintain the
pressure within the set point. the purpose of pressure relief valve shown in red arrow, is to
open or close according to the controller, for example, if the pressure indicator indicate that
the pressure exceed the set point then the controller will transmit signals to the pressure relief
valve to open to reduce the access pressure and bring the reactor back to the desired pressure.

56
 2) Temperature Process:

In urea reactor, temperature changes with the time, thermocouple-type temperature

controllers are used to measure the temperature electronically, finding the temperature change
from the sensor and sending the measured data to the electronic processor. In case of cooling
water in, if the temperature inside the reactor increases than temperature indicator will
transmit the signal to temperature indicator controller to control the control valve of the
cooling water in to open so that more chilled water can go around the reactor to maintain
reactor isothermal conditions.

1. Flow Process

The flow of CO2 and NH3 inlets shown in figure 12 will use the ratio method to maintain the
flow ratio of the two components because CO2 and NH3 are in stoichiometric ratio where two
moles of ammonia will reacts with one mole of CO2 to produce the desired products. When
the flow transmitter measure the flow rate of CO2 in the pipeline and transmit the signal to
the flow indicator than it will control the control valve to allow the desired amount of the
CO2 to go into the reactor through compressors and same method is applied to the NH3.inlet
stream.

13 Plant Layout

13.1 Industrial land prices and site selection:

Figure 13 shows the price of land in different areas of England. It is clear that the North East
is relatively cheap; therefore the plant will be located in this area. There is also a relatively
high abundance of skilled workers in this region which means that staffing the plant should
not be an issue. In order to reduce the environmental impact the site will be developed on a
pre-existing site. Hazardous process must be situated at a safe distance from others building.
Plant site also accommodate disposal of waste into a land or sea, taking this factor into
consideration, North East area have sea or land for waste processing. Plant location in a
remote area is big advantages.

57
 Price of Land (/hectare)
North West
Midlands Price of Land
(/hectare)
North East
South East

0 500 1000 1500

Thousands

Figure 13: Land prices in England

13.2 Plant Layout and other consideration

The principal factor needs to consider for the plant layouts are process requirement,
maintenance convenience, construction/operating costs, process requirements, and safety. A
perfect plant design will be made with high performance and negligible shutdowns. In the
plant layout (see appendix 1) urea plant will be built near to the control room leaving enough
distance in a safe position and also to reduce the wiring cost. Sufficient working space and
head rooms is provided to allow easy access to equipments. The utilities should be located in
the middle between the urea and ammonium sulphate plant to reduce the piping cost and to
make the plant more economical suitable and also it will be easier for both plant to access
utilities. NH3 feed tank are located between urea and ammonium sulphate plant to save the
space and provide easy access for both plants. Sulphuric acid storage tank is located near to
the ammonium sulphate plant and leave the enough space for the driveway because of its
toxicity in case of leakage. Office, workshops and laboratory are located close to each others
and away from the ammonia and sulphuric acid storage tanks in order to provide enough
safety for the workers. It was decided that the fire station will be situated near to the both
plants to provide facilities in case of emergency like fire explosion and shutdown. Store
facilities are provided for any mechanical, instrumentation parts etc. needed for both plants.
Enough space is given for the truck around the plants to provide raw materials for both plants
and to other buildings. Expansion of the plant was also taken into consideration and therefore
all the equipments were conveniently tied accordingly.

13.3 Plant emergency shutdown and start-up Procedure

Emergency shutdown manual will be issued to all the employees working onsite. All the
emergency valves should be closed and turned off the main supply of CO2 and NH3 coming
to the reactor to protect the plant from further exothermic reaction taken place between CO2
and NH3 which will help to reduce the temperature inside the plant and ultimately prevent the

58
urea plant from explosion etc. Emergency alarms should turn on to informed others to escape
from the reactor place. Close down the valve of recycle streams of carbamate and CO2 and
NH3 streams. In case of start-up procedure, allow CO2 and NH3 feed valves and all the
recycle streams valves turn back on and to allow to maintain the reactor temperature.

14 (LOPA) Layer of Protection Analysis

Layer of Protection Analysis (LOPA) is Process Hazard Analysis (PHA) tool. This method
utilizes the initiating events, initiating events likelihood, initiating events causes and impact
events identified during the Hazards and Operability Analysis (HAZOP). LOPA takes the
results from HAZOP and set Safety Integrity Level (SIL) by taking the process to the safe
state when predetermined conditions are violated. This method allows the users to determine
the risk associated with the hazardous events by utilizing the severity level and likelihood of
the initiated event. Typical Excel sheet can be used in order to find the required SIL.
Different industries have their own set risk standards and the users can determined the
amount of risk required and analyse the risk reduction that can be achieved by using
Independent Protection Layers (IPLs) as shown in figure 14. If the additional reduction risk is
still required than, Safety Instrumented Function (SIF) like, fire alarms, Pressure Relief
Valves may be required. The safety integrity level (SIL) of SIF is determined from the
additional risk reduction required. SIL is measure of safety integrity or Probability of Failure
on Demand (PFD) for SIF systems. SIL have four discrete safety levels for given ranges of
PFDs (see appendix 7).

Figure 14: Independent Protection Layers

59
Lower the PFD will be for higher SIL and vice versa. SIS is designed to prevent system from
hazardous event by taking the process to safe state when predetermined condition are violated

BPCS is used during normal operation. Input signal from the operator are generated into the
process output which make the process operate in a design manner. For example, in case of
urea reactor, the process input signals to the output as high pressure it will initiate the action
by maintain or stabilizing the temperature.

The safety life cycle defined in International Electro technical Commission (IEC) 61511-
1requires to determine the SIL for the design of safety-instrumented function. LOPA team
should consists of

Operator having experience in operating the process and risk analysis specialist

Senior process , process control engineer, instrumentation and control and electrical
maintenance engineer

LOPA was carried out on one of the HAZOP node when there was a high temperature and
pressure in the urea reactor due to the loss of cooling water from cooling jacket. Using the
LOPA methodology (see appendix 5) SIL 1 was calculated (See appendix 6 column 14)
which proves that more independent layers of protections and ultimately more money
required bringing the reactor to safe level and to increase SIL1 to SIL4.

14.1 Current Industrial Problems in using HAZOP/LOPA interface

5.1 HAZOP Issues
Companies like JACOBS uses Excel sheet to apply LOPA from HAZOP data. LOPA use
single consequence every time from the HAZOP and find the required SIL level. It is not
difficult to calculate SIL level on different causes and consequences and to find independent
protection layers to safe the plant. However this practise become tedious and time consuming
when same impact events (consequences) are identified for different causes for example, in
case of urea reactor, blockage in the ammonia pipe or any fault in control valves will result in
rupture in the pipe due to high pressure as consequences which means different causes will
result in same consequence. LOPA team wants to find a way to lists all the causes which
leads to the same consequence so that the time can be save to identify all the same causes and
lists together and apply LOPA at once rather than applying LOPA each time. Using this
technique can overcome to time consuming effort as a result more money can be save. But it

60
is very difficult to use this technique using excel sheet for LOPA calculations but some of the
following recommendations can be applied.

Recommendations
This problem could be overcome by using a combination of keywords and lists all the typical
causes for deviation and group under the relevant keywords combinations (i.e. no flow, more
pressure etc.). In other words there is a listing of all the potential problems cause by FLOW
NO or MORE PRESSURE etc. during HAZOP review if the team is having a problem in
identifying the potential deviations, the causes database can easily be interrogated. The
database may easily be amended or expanded so that it becomes a repository of information
that can be accessed during study. The program will automatically display the page that is
relevant to the keywords combination. OR

Create a spread sheet for most common cause and consequences and link it with HAZOP
software so that if the same problems come up you can go into the spread sheet and choose
via hyperlink instead of inputting the data each time.

Overall Conclusion

Process 1 (Urea production via Snamprogetti process and ammonium sulphate production via
H2SO4) is chosen as final process as compared to process 2 due to high profit of process 1
65 million/year as compared to process 2 (profit 54 million/year). Overall mass balance
was carried out where, 80% of ammonia goes to produce 60%of urea and 20% is used up for
40%of ammonium sulphate production. Volume of the urea reactor was found to be 145.5m3
with length of 27m and diameter of 2.61m. 27 sieve plates were used to achieve 34% of urea
product. Optimum operating conditions for urea reactor were 140 bar and 180C with
residence time of 16.7seconds. Hemispherical heads were used for top and bottom ends of the
reactor and half pipe cooling jacket was used to maintain the reactor isothermal conditions.
Stress analysis determined that the reactor can withstand the combined load at higher
operating conditions. The capital cost of the plant and its attachments is 4855059.7 which
is well enough in the range of current urea reactor prices. HAZOP was carried out to
identified the hazards and safeguards/actions needed to protect reactor against different
consequences. LOPA was applied on one the HAZOP consequences to determine the Safety

61
Integrity Level (SIL) for the worst case scenario. Current industrial problems to transfer data
from HAZOP to LOPA were also considered and some recommendations were made in order
to determine the SIL level and to satisfy the clients requirement.

62
 References
Craymer , L. (2009, 09 12). http://www.icis.com/resources/news/2009/10/12/9254331/qafco-to-
construct-610m-urea-plant-in-qatar/. Retrieved 2014, from http://www.icis.com:
http://www.icis.com/resources/news/2009/10/12/9254331/qafco-to-construct-610m-urea-
plant-in-qatar/

McCollum, D. L. (2006). Techno-Economic Models for carbon dioxide compression,transport and

storage . California: WEB: http://its.ucdavis.edu/.

MORIKAWA, H., & SAKATA, E. (n.d.). Mega-capacity Urea Plants-TECs Approach.

Perry, R. H. (1997). Perrys Chemical Engineer's Handbook. US: Mcgraw Hill.

/www.bkvthermal.com. (2007). Retrieved April 2014, from http://www.bkvthermal.com.

Bozzano, G., & M, D. (2003). New internals for urea production reactors. Chemical technology and
biotechnology, 128-1233.

Brouwer, M. (2009). UreaKnowHow.cow. Urea leack detective system.

Choudhari, A. J. (2014). Insulation Materials . Insulation Materials.

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http://www.freecurrencyrates.com/exchange-rate-history/GBP-USD/2010:
http://www.freecurrencyrates.com/exchange-rate-history/GBP-USD/2010

Dente, M., & Rovaglio, M. (1992). Gas-Liquid Reactor in the Synthesis of Urea. Gas-Liquid Reactor
in the Synthesis of Urea, 2475-2480.

Gooneratne, S. (2013). Reaction Engineering and Mass Tranfer.

Hardy, F. (1957). Ammonium Sulfate by the Gypsum Process. Retrieved October 20, 2013, from
http://pubs.acs.org/doi/pdf/10.1021/ie50566a005

Hertanu, H., & Molnar, F. (2005). Chemical Reactors: Basic Control Strategies. 1-5.

Juneja, D. (2013). Fabrication of Construction Materials in Urea Manufacturing Plants. International

Journal of Enhanced Research in Science Technology & Engineering,, 55-56.

L.Fiala. (2006). Thermal conductivity of mineral wool materials partially saturated by water. Thermal
conductivity of mineral wool materials partially saturated by water, 1214-1215.

McKetta, J. J. (1992). Heat Tranfer Design Method. New York: Marcel Dekker.

MORIKAWA, H. (n.d.). Mega-capacity Urea Plants . Toyo Engineering Corporation .

Octave, L. (1999). Chemical Reaction Engineering. New York: John Wiley and Sons.

Richardon, C. a. (2009). Chemical Engineering Design. Burlington USA: Butterworth-Heinemann.

Russell, P. (2013). Group Design Project.

Sinnot, R., & Towler, G. (2009). Chemical Engineering Design. Oxford: Butterworth-Heinemann.

63
Sinnott, R., & Towler, G. (2009). Chemical Engineering Design (Richarson and Coulson V6. edition
5). Oxford: Butterworth-Heinemann.

Snamprogetti. (2014). The snamprogetti Urea Technology. The snamprogetti Urea Technology, 1-4.

Stamicarbon. (2014). Transofrmation the urea process with continuous innovation . Stamicarbon pur
knowledge, 11-25.

Xu, S., & Wang , W. (2012). A Modified Weld Structure of Layered Urea Reactor Based on Stress
Analysis and Leak Detection. Shandong.

Zahradnik, J. (1993). Chemical Reactors for Gas-Liquid Systems. Prague: House of the academic of
sciences of the Czech Republic.

Zardi, F. (2003). New internals for urea production reactors. chemical technology and biology, 128-
133.

Perry, R. H. (1997). Perrys Chemical Engineer's Handbook. US: Mcgraw Hill.

/www.bkvthermal.com. (2007). Retrieved April 2014, from http://www.bkvthermal.com.

Brouwer, M. (2009). UreaKnowHow.cow. Urea leack detective system.

Choudhari, A. J. (2014). Insulation Materials . Insulation Materials.

Gooneratne, S. (2013). Reaction Engineering and Mass Tranfer.

Juneja, D. (2013). Fabrication of Construction Materials in Urea Manufacturing Plants. International

Journal of Enhanced Research in Science Technology & Engineering,, 55-56.

L.Fiala. (2006). Thermal conductivity of mineral wool materials partially saturated by water. Thermal
conductivity of mineral wool materials partially saturated by water, 1214-1215.

Richardon, C. a. (2009). Chemical Engineering Design. Burlington USA: Butterworth-Heinemann.

Sinnott, R., & Towler, G. (2009). Chemical Engineering Design (Richarson and Coulson V6. edition
4). Oxford: Butterworth-Heinemann.

Zahradnik, J. (1993). Chemical Reactors for Gas-Liquid Systems. Prague: House of the academic of
sciences of the Czech Republic.

Bozzano, G., & M, D. (2003). New internals for urea production reactors. Chemical technology and
biotechnology, 128-1233.

Dente, M., & Rovaglio, M. (1992). Gas-Liquid Reactor in the Synthesis of Urea. Gas-Liquid Reactor
in the Synthesis of Urea, 2475-2480.

Gooneratne, S. (2013). Reaction Engineering and Mass Tranfer.

Hertanu, H., & Molnar, F. (2005). Chemical Reactors: Basic Control Strategies. 1-5.

Octave, L. (1999). Chemical Reaction Engineering. New York: John Wiley and Sons.

64
Richardon, C. a. (2009). Chemical Engineering Design. Burlington USA: Butterworth-Heinemann.

Xu, S., & Wang , W. (2012). A Modified Weld Structure of Layered Urea Reactor Based on Stress
Analysis and Leak Detection. Shandong.

Zahradnik, J. (1993). Chemical Reactors for Gas-Liquid Systems. Prague: House of the academic of
sciences of the Czech Republic.

Zardi, F. (2003). New internals for urea production reactors. chemical technology and biology, 128-
133.

65
Appendix1: Plant Layout and Process 2 (Urea (Stamicarbon) and ammonium sulphate using gypsum

66
Appendix 2: Decision Analysis and DOW Index for Fire and Explosion

67
Appendix3: Urea and Ammonium Sulphate plant PFD, capital cost and Payback time

68
 Appendix 4 : Mass flow and Energy Flow table for Urea and Ammonium Sulphate Plant
component 1 1a 1b 2 3 4 5 6 7 8 8a 9 9a 10 11 12 13 14 15 16 1 18
7

818.
Biuret 818 818 818 818 0363 818

8016 8016 8016 8016 8016

Urea 80167 7 7 7 7 7

5
9
4
8 3130.9
Co2 8 7 3130 1565 3130

763 458 14 149 1.4 1.4 1.

88 33 92 22 5
Ammonia 2 2554 2554 1277 2554

24336. 2433 2433 2433 22674 1661 843 818 45 4 4 0.5

Water 18 6 6 6

Carbamat 12477 12477 12477

e 9 9 9

H2SO4 4301 43
1 390 434 43

(NH4)2SO 577 577

4 583 58324 41 41

69
Total mass 763 458 14 5 23578 12477 1110 12477 1081 1053 22674 8264 843 8180 5685 149 4301 58804 577 5. 577
(kg/h) 88 33 92 9 6 9 07 9 64 21 6 3 22 1 89.4 5 84
2 4
8
8 973

H(kj/h) 152 - 1 14383 94933 1794 94933 9606 1251 4157 9160 138 2090 473 29202 287 1 615
762 18 6 8346 420 5601 420 3457 2865 71 30 684 574 69. 01 280 5 503
9 81 6 4 7 8 2 6
56 4 8.
2 2 4
0 1
7 6
8

Temperatu 40 - 4 180 180 190 180 140 80 27.2 26 30 60 60 60 60 50 1 100

re (C) 58. 0 5 0
5 0

70
 Appendix 5: LOPA terms explanations and method of calculations for SIL
Impact event Severity levels Initiating causes Initiating Protection layers Intermediate SIF integrity level Mitigate event
likelihood event likelihood likelihood

Impact events are Severity levels Which cause The frequency of Protection layers From appendix 6,, If new SIL is Mitigated event is
the HAZOP could be minor, impact events, initiating cause require protecting it was calculated required than calculated by
consequences. sever or Impacts events per year. From the system hazard by multiplying by dividing the multiplying
From appendix 6, extensive. From might have many appendix 6, it was and bringing back to column 4 with corporate integrity Column 10 and 11
High pressure in the appendix 6,, initiating causes. decided that required reduction Column (5, 6, 7, 8 level criteria by the see appendix 6,
urea reactor may selected severity From appendix 6, cooling jacket level. Protection and 9). If the intermediate event
cause rupture or level is Serious the initiating failure happened layers that have high calculated risk is likelihood, and
explosion which (S). causes are loos of once in every ten degree of reliability less than the PFD for SIF is
can cause fatalities, cooling jacket years so the are classified as corporate criteria selected as a
fire if ignition water. frequency would impendent for this severity maximum below
sources are located be 0.1 per year. protection layer level than this number and
near to the reactor. (Shown in figure additional layers entered in Column
Toxic ammonia and 14). From appendix are required. 10 From appendix
carbamate will 6, due to explosion 6,
cause seriously proof electrical
damage to the classification, it was
locals. decided that the
hazard was reduced
by the factor of 10,
thats why 0.1 was
decided due to
management control
system. 0.1 PFDs
was used for fire
alarm, control loop
and relieve vlave .

71
Appendix 6: SIL calculations for one of the HAZOP node.

# 1 2 3 4 5 6 7 8 9 10 11 12 13 14

Independent Protection Layers

Impact Severity Initiating Initiating General Basic Alarms Relieve Intermediate SIF Mitigat Notes SIL
event level causes cause Process valves, event likelihood integrity e event
likelihood Process Control level likeliho
design Systems Restricted od
(BPCS) access

1 Fire S Loss of 0.1 0.1 0.1 0.1 0.1 10-5 10-2 10-7 High 1
from cooling pressure
urea water and
reactor from temperature
cooling in the urea
jacket reactor
cause
rupture and
explosion

72
Appendix 7 : PFDs for required SIL, Colour coded HAZOP diagram, Residence time Calculations

73
 Appendix 8: Full HAZOP Analysis

Node 1 - Ammonia Stream to Reactor

Parameter Deviation Possible Cause Consequence Actions
Flow No Pump suction/discharge valve i) Potential pump failure. a) Automatic switch over to
closed in error or flow ratio standby pump
control failure (closes valve) or
pump fails

b) Introduce high level alarm

on ammonia storage tank.
ii) Potential overfill of upstream ammonia storage tank. Loss of a) Introduce High level trip on
containment of ammonia liquid leading to toxic release. Safety ammonia storage tank.
impact & environmental loss of containment and toxic impact on
aquatic life.
iii) Downstream consequence - Reduce reaction rate therefore no a) Introduce ambient ammonia
hazard. Commercial impact due to reduced quality in product. monitors to detect vapours to
alert site personel to leak
b) Introduce ammonia
detectors in drainage system
to alert to liquid spill (tank
overfill)
Flow More Two pumps running i) Upstream - Loss of level in upstream ammonia storgae tank, a) Automatic switch over to
simultaneously due to operator ultimately leading to cavitation of pump Standby pump
error or flow ratio control failure
(drives flow control valve fully
open) 74
b) Confirm whether water
cooling jacket has the capacity
to cope with the worst case
reaction in the reactor
 ii)Downstream - Excess ammonia to reactor, leading to pressure a)Introduce high temperature
increase in reactor ultimately leading to overpressurisation of the and high pressure alarms on
reactor causing mechanical failure and loss of containment of reactor
ammonia. Toxic impact and potential multiple fatalities.
b) Introduce high temperature
and high pressure trips on
reactor - tripping all feeds to
reactor (ammonia, co2,
recycles streams)
c) develop emergency
response measures including,
toxic gas refuge, ammonia
detectors, wind sock (to
inform which direction the
plume would move)
d) install relief valve on reactor
and ensure it is sized for
overpressure case
e) Introduce low level alarm on
ammonia storage tank
f)Introduce low level trip on
ammonia storage tank
consequently tripping pump
Temperature High Pump discharge valve closed i)High temperaure in the pump (centrifugal pump) leading to a) Automatic switch to standby
potential pump damage pump E-14
Temperature Low No credible Causes Identified - -
Pressure High Failure of upstream valve i) Mechanical pipeline failure on node 1 a) Pressure system trigger
relief valve to container
Pressure Low Failure of Pump i) No flow to reactor a) Auto switch to standby
pump E-14
Node 2 CO2 Supply to Reactor
Parameter Deviation Cause Consequence Action
Flow No Compressor fails i) Same scenario as more flow node 1, excess a) Same as scenario more flow node 1.
ammonia.

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 No Compressor suction valve closed
in error or flow ratio controller
failure driving the flow control
valve closed
No Compressor discharge valve
closed in error
Flow More Two Compressors running
simultaniously due to operator
error or flow ratio control failure
(drives flow control valve fully
open)
Temperature High No credible Causes Identified
ii) Low compressor suction pressure leading to
possible compressor damage
iii) Compressor continues to run overpressurising the
discharge line leading to potential discharge line
failure & loss of contaminent of CO2. Potential
asphyxiation and toxic hazard. Potential fatalities
i) Upstream - Loss of level in upstream carbon dioxide
storage tank, flooding reactor with carbon dioxide.
Reduce reactor temperature and reduce product
quality.
ii)Downstream - Excess carbon dixoide to reactor,
leading to pressure increase in reactor ultimately
leading to overpressurisation of the reactor causing
mechanical failure and loss of carbon dioxide.
Potential asphyxiation and toxic hazard. Potential
fatalities.
-
a) Introduce a low pressure trip on suction
side of compressor
a) Asphyxiation hazard can be removed if
the plant layout is not congested and
there is no containment.
b) Introduce high level alarm on pipwork
between compressor and discharge valve.
c) Introduce high high level alarm to trip
compressor
d)introduce pressure relief valve sized for
blocked discharge of compressor, vent to a
safe location.
a) Automatic switch over to Standby
pump.
a) Asphyxiation hazard can be removed if
the plant layout is not congested and
there is no containment.
b) Introduce high temperature and high
pressure trips on reactor - tripping all
feeds to reactor (ammonia, co2, recycles
streams)

Temperature Low No credible Causes Identified - -

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 Pressure High No additional causes identified - - -
See High pressure on node 1

Pressure Low No additional causes identified - - -

See High pressure on node 1

Node 3 cooling water supply & return from reactor.

Parameter Deviation Cause Consequence Action
Flow No Cooling water pump stops or i) Loss of cooling water to reactor leading to increased temperature a) Introduce a low flow alarm
valve closed in error and possible run away reaction. See node 1 more flow for precedure. on cooling water supply.
b) Introduce low level alarm
on cooling water supply.
c) Follow - More Flow (ii)
actions
Flow More Two cooling pumps running i) Lower reaction temperature and possible reduction in product yield a) Introduce a high flow alarm
simultaneously on cooling water supply

Temperature High High temperature in cooling i) Increased reactor temperature, possibly leading to reactor run a) Introduce temperature
water storage tank away. indicator on reactor outlet to
alter cooling water flow.
Temperature Low Low temperature in cooling i) Reduced reactor temperature a) See Temperature High for
water supply action

Increased flow of cooling i) Reduced reactor temperature a) Auto switch to standby

water to jacket, valve stuck pump - E-24
open in error.
Pressure High Closed valve on cooling jacket i) Possible mechanical failure, flooding reactor area with hot water a) Auto switch to standby
outlet likely to cause injury. pump - E-24
Pressure Low No Credible Cause Identified
Node 4 - Recycle Stream to Reactor
Parameter Deviation Cause Consequence Action
Flow No No additional cause needed - See Flow No Node 1

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 Flow More No additional cause needed - See Flow More Node 1
Temperature High No credible Causes Identified
Temperature Low No credible Causes Identified
Pressure High No additional causes needed - See Pressure High Node 1

Appendix 9: HAZOP to LOPA data transfer, Mechanical/chemical safety sheet

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