Chemical Technology & Equipment Design

Group project - Review of technologies and Preliminary Economic Analysis

For production of ​350000 TPA​ of ​Urea​ at ​Tuticorin​ -​ Group 10

CH16B055- Prashanth Ravula
CH16B119 - Vasistha Singhal
CH16B062 - Sakshi Gupta
CH19E002 - Dnyanesh Deshpande

Technology 1: Snamprogetti process

Raw materials required: -

N H 3 (99.5 % pure, obtained f rom haber′s process ) ​ ​

[​1]

C O2 (97.6 % pure, obtained f rom membrane separation of air) ​ ​

[2]

Process description​: -
● N H 3 & C O2 are compressed using a high-pressure pump and an isentropic
compressor respectively. After compression both the streams are made to exchange
heat in a heat exchanger.
● Now the N H 3 & C O2 streams are fed into the reactor at high temperature and pressure
where they react to form Ammonium Carbamate.
● This ammonium carbamate formed undergoes dehydration to form urea
● This urea solution containing urea, water, ammonium carbamate, unconverted N H 3 &
C O2 are fed into a stripper
● From the stripper the urea solution is sent to the medium pressure decomposer where
urea purification takes place by dehydration of carbamate. Further purification of urea
takes place in the low-pressure decomposer.
● From MP and LP decomposers the urea is sent to MP absorber and MP condenser for
recovery of unconverted ammonia. After that the urea solution is sent to the Vacuum
evaporators for further concentration.
● Now molten urea is sent to prilling tower where urea prills are formed by passing
currents of cold air from the bottom of the tower. The proper size urea prills are sent to
the bagging section through belt conveyors. In the bagging section coating of urea may
be done if required (neem coating).
Reactions Involved: -

​Main reaction​: - Formation urea from NH3 & CO2

● 2N H 3 + C O2 →N H 4 COON H 2
(ammonium carbamate)

● N H 4 COON H 2 → N H 2 CON H 2 + H 2 O
(urea)

Side reaction​: - Formation of Biuret

● 2N H 2 CON H 2 → N H 2 CON HCON H 2 + N H 3
(biuret)

Material Balance: -

The given capacity of the plant =​ 3,50,000 TPA of urea

= (3,50,000*1000)/365 kg/day of urea

= 958904.1096 kg/day of urea

= 15981.73516 kmol/day of urea

The composition of urea (% w/w) produced is

● 99.6% urea ​ [3]

​
● 0.4%biuret ​ ​[4]

So, the amount of urea = (0.996) *(958904.1096) = 955068.4932 kg/day = 15917.80822

kmol/day

Amount of biuret = (0.004) *(958904.1096) = 3835.616438 kg/day = 37.23899455 kmol/day

Amount of urea required to form 37.23899455 kmol/day of biuret = (2) *(37.23899455) =

74.47798909 kmol/day

Total ​amount of urea produced​ = 15917.80822 + 74.47798909 = ​15992.28621 kmol/day

Ammonium carbamate required to form 15992.28621 kmol/day of urea = 15992.28621

kmol/day
 Amount of C O2 required to form 15992.28621 kmol/day of ammonium carbamate
=15992.28621kmol/day
[5]
Taking conversion of C O2 to be 60 %, we have​

Amount ​CO​2​ required​ =15992.28621/0.6 =​ 26653.81035 kmol/day

Amount of ​NH​3​ required ​is = (2) *(26653.81035) = 5

​ 3307.6207 kmol/day

As N H 3 is 99.5% pure then actual amount of​ NH​3​ required​ =53307.6207/0.995 =​ 53575.49819
kmol/day

As C O2 is 97.6 % pure we have actual amount of ​CO​2​ ​required​= 26653.81035/0.976 =

27309.23192​ ​kmol/day

Economic Analysis: -

Cost of 99.5% pure N H 3 = Rs.15/litre = Rs.16.6/kg = Rs 16600/ton [6]

​

Sourced at Tuticorin factory, so ​no transport cost [14]

​

Density used = 0.903g/cm​3

Cost of 97.6% pure C O2 = Rs.1.8/kg ​ ​

[7]

Cost of 99.6% urea = Rs.34/kg​[9]

Molar
Mass Input Output Net Net Price Cost
Chemical (g/mol) (kmol/day) (kmol/day) (kmol/day) (ton/year) (Rs/ton) (Rs/year)

Ammonia 17 53575.49819 37.23899455 53538.2592 332204.8983 16600 5514601312

Carbon
dioxide 44 27309.23192 10923.69277 16385.53915 263151.7587 1800 473673165.7

Urea 60 0 15981.73516 15981.73516 350000 34000 11900000000

Inert 923.2990569 923.2990569 0 0 0 0

Total cost​ = Rs.5988274478/ year =​ Rs. 598.82 crores/year

Total Revenue​ = Rs.11900000000/ year =​ Rs. 1190 crores/year
Net Profit​ = Rs.5911725522/year =​ Rs. 591.17 crores/year
ROI = 98.72%
Technology 2:
Production of Urea using Carbonyl Sulfide and Ammonia in presence
of Methanol

Introduction:
Conventional process of manufacturing urea involves subjecting a mixture of carbon dioxide and
ammonia to an elevated pressure and temperature. Although the carbon dioxide process has
been in commercial use for a number of years, it has its drawbacks. One serious drawback is
that the cost of building and operating the plant is very high because of the high pressure
required. An additional drawback is that the yields are undesirably low.

Another conventional process of producing urea comprises subjecting a mixture of carbonyl

sulfide and ammonia to a pressure of 300-566 psi and a temperature of 110 C-120 C​[10]​. Under
these conditions an intermediate product, ​ammonium thiocarbamate​, forms as a precipitate
and is converted to urea. Although yields up to approximately 70% urea are reported for this so
called carbonyl sulfide process, the art has not developed the process beyond a very small
laboratory scale. Likewise one major difficulty with this process is the high pressure required.
Because the ammonium thiocarbamate is in a solid state, another difficulty involves handling it.
A further difficulty is that at least one and preferably both of the reactants must be liquefied in
order to accelerate the reaction.

It has been found by employing methanol that the ammonium thiocarbamate dissolves therein
as fast as formed and thereby greatly improves the process from an engineering or handling
standpoint. There has also been a marked increase in the yields of Urea at lower pressures and
temperatures

Reactions

The Process:

Ammonia gas is mixed with anhydrous methanol and the resulting solution is mixed with
carbonyl sulfide gas, the molar ​ratio of ammonia to carbonyl sulfide​ being greater than ​3:1​.
Thus at room temperature the intermediate product, ammonium thiocarbamate, is formed.
almost instantaneously. The ammonium thiocarbamate is converted to urea by subjecting in a
closed system the mixture thus formed to a temperature of 80​o​C-120​o​C​[10]​ and the autogenous
pressure developed until the reaction is substantially complete. Then the methanol is removed
by distillation. During the distillation of the methanol the ammonia and sulfur values are also
driven off and may be recovered, thus leaving the urea behind. The distillation may be
continued to the point at which urea crystallizes from solution or the mixture may be completely
evaporated to dryness and the urea crystallized from fresh methanol.

Operating conditions:
40°C- 140°C and a ratio of 1.84-39.0 moles ammonia per mol of carbonyl sulfide. Pressure -
atmospheric​[10]
Raw materials:
Ammonia, Carbonyl Sulfide, Methanol
Products:
Urea, hydrogen sulfide

Through experiments, they have determined that when the molar ratio of NH3/COS is 2.74,
runtime 3 hours at 80​o​C, the yield is 83.8%​[10]

Material Balance

2.74 moles of NH​3​ + 1 mole of COS gives 0.838 mol of urea

46.58 g NH​3​ + 60 g COS = 57.408 g Urea
The given capacity of the plant =​ 3,50,000 TPA of urea

= (3,50,000*1000)/365 kg/day of urea

= 958904.1096 kg/day of urea

= 15981.73516 kmol/day of urea

Ammonia requirement: 47106.069 kmol/day of NH​3

As ​NH​3 is 99.5% pure, ​requirement = 47106.069/0.995 kmol/day = 47342.7829 kmol/day =

804827.3093 kg/day

COS requirement = 19071.283 kmol/day

As ​COS is 99.5% pure, ​requirement = 19071.283/0.995 kmol/day = 19167.11859 kmol/day =

1150027.11557 kg/day

Economic Analysis:

Cost of 99.5% pure N H 3 = Rs.15/litre = Rs.16.6/kg​[6]

Cost of 99.5% pure COS = Rs.4200/ kg​[11]

 Selling price of Urea = Rs 34/kg​[9]

Selling price of H​2​S = Rs. 5000/kg​[12]

Molar mass Input Output Net Net Price Cost

Chemical (g/mol) (kmol/day) (kmol/day) (kmol/day) (ton/year) (Rs/ton) (Rs/year)
NH3 17 804827.3093 0 804827.3093 4993953.45 16600 82899627340
COS 60 19167.11859 0 19167.11859 419759.89 4200000 1762991567908
Urea 60 0 15981.73516 15981.73516 350000 34000 11900000000
H2S 34 0 15981.73516 15981.73516 350000 5000000 1750000000000

Total cost​ = Rs. 1845891195248/ year = ​Rs.184589.11 crores/year

Total Revenue​ = Rs.1761900000000/ year =​ Rs.176190 crores/year
Net Profit/Loss​ = -Rs.83991195248/ year =​ - Rs. 8399.11 crores /year

We find that this process is ​not profitable in a large-scale setting​.

Technology 3:
Production of Urea using Natural Gas and Bosch-Haber’s Process

Description and Reactions:

Holistic overview of Urea synthesis​[17]

Two-fold method
1. Ammonia Synthesis​ from Natural Gas and Steam with certain processes like
desulfurization and combustion.
2. Urea Synthesis ​from leftover CO​2​ and the ammonia produced in the step 1.

Raw Materials required:

Natural Gas(87% Methane), Steam, Air
Catalysts required:
ZnO, Ni, Cobalt Molybdenum Catalyst, FeO, Fe, glycol dimethylether / propylene carbonate,
CuO, Cr​2​O​3​/FeO.
Schematic representation of urea synthesis
The Process:​ ​[16]

● For large scale production of ammonia, the feedstock which makes up the reactants are
water, methane and air.
● H​2 is formed by reacting natural gas and steam at high temperatures and the N​2 is
supplied from air. (water and CO​2​ are removed from the gas stream).
● Then, ammonia is produced through ​Haber’s Process.

Haber’s Process
● H​2 & N​2 is passed over Fe catalyst at medium temperature(~500 C) and high
pressure(~250 atm).
● Porous​ iron catalyst​ derived from magnetite Fe​3​O​4​ is used as a catalyst.
● Yield is around ​10-20%​( assumption - 20%)​[15]​. Reaction is exothermic in nature.

Desulfurization
● Natural gas contains some sulfurous compounds which damage the catalysts used in
the process. They are removed by reacting them with ZnO in the presence of ​Co-Mo
catalyst.

● H​2​ required here is generally recycled from the synthesis gas.

Gas from desulfurizer is sent to ​primary reformer​ for steam reforming (ratio: steam/gas=3:1)
Large number of ​high-Ni-Cr alloy​ tubes are used.
● Superheated steam reacts with Methane at ​770 C​.

● This gaseous mixture is known as ​synthesis gas.

● Yield is 30-40% (assumption - 40%) [16]
● Temperature is increased to increase the conversion, which is done in the ​secondary
reformer ​by internal combustion of part of the gas with process air, which also provides
for N​2​ for final synthesis gas.
● Ni ​catalyst is used for this process.
 ● Further heating of 600 C, and the outlet temperature ~ 1000 C and upto 99% of
hydrocarbon feed is converted.
● Gas is further cooled to 350-400 C.

As the catalyst used in Haber’s Process is Fe, excess CO and CO​2 must be removed to prevent
oxidation of iron.

This is done by the 3 steps listed below:

● Shift Conversion
● 12-15% CO from secondary reformer is converted to CO​2 in the ​High Temperature
Shift ​(HTS) Conversion.
● The gas is passed through a bed of ​Cr​2​O​3​/FeO​ at 400 C.
Co content reduces to 3%.

Gas is further passed through ​Lower Temperature Shift ​(LTS)

CuO/ZnO catalysts are used at 200-220 C
Residual CO content is ~0.2-0.3%.

Condensate
Most of the synthesis gas after removal of CO is cooled and the steam is condensed before
removal of CO​2 ​(Now contains H​2​, N​2 &
​ CO​2​).
Minor amounts of ammonia, methanol, formic acid and acetic acid are stripped from the
condensate.
● CO​2​ Removal
This step removes CO​2​ from the reaction gas by absorption in physical solvents.
Solvents used are ​glycol dimethylethers ​and ​propylene carbonate ​which reduce the
concentration down to 50ppm.
● Methanation
Small amounts of CO and CO​2 remaining in synthesis gas are poisonous for NH​3 ​synthesis
catalyst and must be removed by conversion to CH​4​ in the methanator.

Reactions take place around 300 C in a reactor filled with ​Ni catalyst.

Material Balance:

We work backwards from the main reaction to first find the amount of NH​3 required and from
there we find the amount of H​2 required and then we find the amount of CH​4 required.
​ From
there, we get the amount of natural gas and steam required for the process.
From the mass balance analysis of technology 1, we know the amount of NH​3 required to
produce the target amount of urea.
Amount of ​NH​3​ required​ = ​59528.33 kmol/day

Now, we look at the Haber process to find out the amount of H​2​ required per day.

N​2​ + 3H​2​ → 2NH​3​ (Yield = 20%)​[16]

Using the yield and the stoichiometry,

Amount of ​H​2 ​required​ = 5*(3/2)*59528.33 kmol/day = ​444,462.475 kmol/day

Next, we calculate the amount of CH4 required from the following reactions,

So, taking 70% volumetric yield of H​2​[15]​, and then using a mole balance on the carbon atoms,
we conclude that the amount CH​4 required would be (3/7) times the amount of H​2 produced.
Hence,
Amount of CH​4 required
​ = (3/7)*444,462.475 kmol/day = 191,341 kmol/day

But, in the initial reformation step, the yield is only 40%​[16]​, so

Amount of ​CH​4 ​required​ = 191,341/0.4 = ​478,352.5 kmol/day

Now, we take the composition of Natural Gas to be 87% methane​[18]​, therefore the amount of
natural gas required​ =478,352.5/0.87 = ​549,830.46​ ​kmol/day

And from the process description, we know that the steam and natural gas have to be mixed in
the molar ratio 3:1, so amount of ​steam required​ = 549,830.46*3 = ​1,649,491.38 kmol/day

Economic Analysis:
Cost of natural gas = Rs.2/kg​[19]
Cost of Steam (will be estimated at a later stage using energy balance)
Selling cost of urea = Rs.34/kg​[9]
Cost of ZnO = Rs.57/kg​[20]
Cost of Molybdenum Sulphide catalyst = Rs.2100/kg​[21]
Quantity analysis of catalysts used
ZnO:
 Hydrogenation of Sulfur Compounds is done in the presence of Co-Mb catalyst.
ZnO required = Moles of H​2​S present in Natural Gas (3%)​[18]
= 219,932.25*0.03 kmol/day
= 6597.97 kmol/day

Co-Mo:
An example is used for sample calculation of catalyst required

MoS​2​ is used as the main catalyst

[22]

1 MoS​2​ is required for 1 H​2​S molecule

Hence, MoS​2 ​ required = Moles of H​2​S = ​ 6597.97 kmol/day

Molar mass Input Output Net Net Price Cost

Chemical (g/mol) (kmol/day) (kmol/day) (kgmole/day) (ton/year) (Rs/ton) (Rs/year)
Natural gas 16 549830.46 0 549830.46 8797.28736 2000 17594574.72
Zinc Oxide 81.38 6598 0 6598 536.94524 57000 30605878.68
MoS​2 160 6598 0 6598 1055.68 2100000 2216928000
Urea 60 0 15981.73516 15981.73516 350000 34000 11900000000

Total cost​ = Rs.2265128453/ year = ​Rs.226.51 crores/year

Total Revenue​ = Rs.11900000000/ year = ​Rs.1190 crores/year
Net Profit​ = Rs.9634871547/ year = ​Rs.963.49 crores /year
ROI ​= Net Profit/ Total Cost * 100 = ​425.36%

We find that the ROI is very high but this is because we haven’t estimated the cost of
producing steam, also most of the processes in the intermediate stages require high
temperature and pressure which cannot be considered in this ​preliminary analysis​.
Review and Analysis of Technologies:
Budget: We see that Snamprogetti process gives us an ROI of 98.72% and Natural Gas
method gives us an ROI of 425.36%, whereas Carbonyl disulfide method is not profitable at all

Safety: Production through Natural gas involves very high pressure and high temperature
processes. It also includes methane which is dangerous at such high temperature situations​[23]​.
The other two technologies are relatively safer.

Environmental Impact: ​Production through Natural gas and Carbonyl sulfide give out H​2​S,
which is a pollutant. Snamprogetti process is relatively much more sustainable

Based on the above factors, ​we select the Snamprogetti process

References
(1) http://www.essentialchemicalindustry.org/chemicals/ammonia.html
(2) https://pubs.rsc.org/en/content/articlelanding/2011/ee/c1ee01681d/unauth#!divAbstract

(3) https://nzic.org.nz/app/uploads/2017/10/1A.pdf
(4) http://www.sumobrain.com/patents/wipo/Urea-production-with-controlled-biuret/WO2017
192032A1.pd

(5) https://www.irjet.net/archives/V6/i4/IRJET-V6I484.pdf

(6) http://www.merckmillipore.com/IN/en/product/Ammonia-solution-250-0,MDA_CHEM-105
432?ReferrerURL=https%3A%2F%2Fwww.google.com%2F

(7) https://www.synapse-energy.com/sites/default/files/2015%20Carbon%20Dioxide%20Pric
e%20Report.pdf
(8) https://www.alibaba.com/trade/search?fsb=y&IndexArea=product_en&CatId=&SearchTe
xt=ammonia+liquid

(9) https://www.indiamart.com/proddetail/technical-grade-urea-18093828855.html

(10) https://patents.google.com/patent/US2681930A/en

(11) ​https://www.indiamart.com/proddetail/carbonyl-sulphide-gas-8131072055.html

(12) https://www.indiamart.com/proddetail/hydrogen-sulphide-10674050473.html

(13) https://www.chemicalbook.com/Price/Biuret.htm
(14) https://www.tacfert.in/

(15) https://patents.google.com/patent/US7674932B2/en

(16) https://www.slideshare.net/ZameerAhmedWassan/ammonia-and-urea-production

(17) https://nzic.org.nz/app/uploads/2017/10/1A.pdf

(18) https://www.croftsystems.net/oil-gas-blog/natural-gas-composition
(19) https://www.thehindubusinessline.com/economy/natural-gas-price-may-go-up-by-18-
from-april/article26571591.ece

(20) https://www.indiamart.com/proddetail/zinc-oxide-8318706233.html

(21) https://www.alibaba.com/trade/search?fsb=y&IndexArea=product_en&CatId=&Searc
hText=molybdenum+disulphide

(22) https://en.wikipedia.org/wiki/Hydrodesulfurization

(23) https://www.pge.com/includes/docs/pdfs/shared/environment/pge/cleanair/methane1
033.pdf