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2.1 AMMONIA PRODUCTION COSTS In the mid-1990’s the ammonia industry accounted
for about 5% of the worldwide natural gas consumption. For economic and
environmental reasons, natural gas is the feedstock of choice. However, processes for
ammonia production can use a wide range of energy sources. For example, in 2001 60%
of China’s nitrogen fertilizer production was based on coal. In 2002 natural gas is the
most economic feedstock for the assembly of ammonia as shown in Table 2.1[7] Table
2.1 Feedstock Economics for Ammonia Production (7) _Natural Gas _Heavy Oil _Coal _ _
Energy Consumption _1.0 _1.3 _1.7 _ _Investment Cost _1.0

_1.4 _2.4 _ _Production Cost _1.9 _1.2 _1.7 _ _ Ammonia production costs are very
dependent on feedstock cost – which is normally natural gas. Natural gas prices can vary
significantly from region to region. They may also be impacted by the cycles in the
world energy market. In addition, in regions where natural gas is owned or controlled by
the government, social concerns (such as keeping people employed or generating hard
currency from export sales) can have an impact on natural gas prices.

Typical ammonia production costs are listed in the Table 2.2.[8] Table 2.2 Approximate
U.S. cash production costs for ammonia – 2000(7) Gas Price ($US / Million BTU) _2 _$4
_$6 _ _Gas Use (Million BTU / tonne) _36 _36 _36 _ _Gas Cost ($US / tonne Ammonia)
_$72 _$144 _$216 _ _Conversion Cost ($US /tonne Ammonia) _$28 _$28 _$28 _ _Total
Cost ($US /tonne Ammonia _$100 _$172 _$244 _ _ Natural gas is usually employed both
as feedstock, in order to obtain the necessary hydrogen to form the chemical compound
NH3(non-energy use of natural gas). and as fuel to provide the required energy
.according to gross estimations, approximately 2/3 of consumed Natural gas is used as a
feedstock.while around 1/3 is used for energy puepose.
Natural gas is the key cost driver for the ammonia industry as, depending on its price, it
makes up approximately 70-85% of the ammonia production costs (see Figure2) Fig-
2-Ammonia Fig-2.1 Ammonia production costs by geographical region(9) Fig-2.2
Ammonia production costs at different natural gas prices.[9]
 Manufacturing Cost. table 1 provides a breakdowa of the estimated manufacturing
cost of ammonia in a 1000 metric tons per day plant bulit in early 1990 on the U.S. Gulf
Coast the fixed investment includes off_sites, consisting of raw water and boler feed
water treatment, ammonia stoage,and a cooling tower.

The working capital includes product storage for 30 days at $150/t Natural gas i
eedstock to a reduced energy anmonia process commescialized in the early 1980. The
20% pretax return on investment is a reasonable expectation for plants located in
Westem economies,where coporate tax on eamings is about 50% Factor _Unit rate /t
_$US/units _Cost,$/t _ _ Variable costs _ _ _ _ _Natural gas (feed-fuel), GJ _28.45 _1.90
_54.06 _ _Boiler feed water make-up, m3 _1.1 _0.25 _0.28 _ _Cooling water circulation,m3
(total temperature = 10C) _210 _0.01 _2.10 _ _Catalyst cost _ _ _1.7 _ _ Fixed costs _ _ _ _
_Labor, personnel shift ($10/h) _6 _10 _1.44 _ _Supervision, 100% of labor _ _ _1.44 _
_Interest on working capital, % _10 _ _1.30 _ _Indirect charges, % _16 _ _44.06 _ _Total
production cost _ _ _106.38 _ _Pretax return on investment (ROI), % _20 _ _55.07 _
_Ammonia cost (FOB plant) _ _ _161.45 _ _Cash cost of production _ _ _78.84 _ _ total
investment of S99,500,00 (U.S. $95 milion in fixed investment and $4.5 million in
working capital)."To convert G to Gcal, divide by 4.184.

Fixed investment includes cooling tower, boiler feed water treatment, raw water
ammonia storage as minimum off-sites requirement. Indirect charges ate 16% of fixed
investment per ton per year 10'% depreciation; 1.5%, insurance, 3V%, maintenance
(labor, materials, 1.5%, general sales and marketingCash cost excludes 10/%
depreciation allowance and 20% pretax ROl. As can be seen from this analysis, the
natural gas feedstock and capital charges amount to over 93% of the
entire generation fetched before return on investment.

Therefore, energy consumption and capital investment are the key factors in
determining ammonia production profitability A natural gas delivered price of $190/GJ
($200/MMB»), on lower heating value (LHV) basis, was reported for February 190 in the
United States(81). obviously, different natural gas prices change the economics. Location
of the ammonia plant influences the fixed investment and can be substantial y higher if a
complete grassroots plant in a country lacking the necessary in frastnucture is built.

In the energy-tich countries of the Near East, in the USSR, and in North Africa, natural
gas prices are on the order of S0.47/GJ (S0.5/MMBu); however, construction cost at
these locations tends to be higher than on the U.S. Gulf Coast. Whereas the
manufacturing cost is strongly influenced by energy prices, cost of money, and capital
investment, ammonia selling paces are usually determined by supply and demand.
Therefore, the profitability of ammonia plants is determined by the margin between cost
of production and ammonia pice. Table 1 shows an estimate of the cash cost of
ammonia of $78.84/t. The FOB price of ammonia on the U.S.

Gulf Coast in late February 1990 was $107/t (81). Therefore, a producer in Louisiana,
Florida, or Texas could have a $28 margin at a natural gas price of $1.90/G]
($200/MMBu) and energy Consumption of $28.45 GJ/t (24.5 MMBtu/ST) However, the
plants on the US. Gulf Coast were built in the late 1960s and eady 1970s and consume
on the order of 34.85 GJ/t (30 MMBu/ST), which gives about $12.00/t higher production
cost or a margin of only $16/t.[12] 2.2 Le Chatelier’s Principle When looking at Le
Chatelier’s Principle, we are able to see that when adding or simply having more moles
on the reactants side than on the products side it will favour the product side which will
make this a forward reaction(H.L.Le chatelier,1884).Also, by decreasing the temperature
meaning that the temperature used is low, it will make the reaction exothermic (forward
reaction) which will let heat being released(H.L.Le chatelier,1888)[13] 2.2.1The
Temperature For the reaction to occur faster, high temperatures should be used.
However, the higher the temperature is, the more dangerous these chemicals can
become which can have effects on human health(Atkins?PW,1993) 2.2.2

Ideal Temperature and Weight This response is more often than not carried out with
moo temperatures indeed in case 400-450 degrees Celsius isn't considered to be so low
it may be a compromise that was exhausted arrange for all the response to require put
since a few reactants are not viable at either tall or exceptionally moo temperatures. The
weight utilized (Pearson New Jersey,1993)(Bailyn,M.1994). 2.2.3 Catalyst Since
temperatures have to be held as low as they possibly can be, an Iron Oxide Catalyst is
therefore used(Freeman,San Francisco,1964)(Jim Clark (chemauide.co.uk). 2.2.4

Still Imperative Nowadays The Haber handle is still critical nowadays since it
produces smelling salts which can be utilized for different things. Alkali can be utilized in
fertilizers and it can moreover be utilized in cleaning supplies that are utilized for glass.
The Haber handle is appeared to be creating around 500million tones of fertilizers each
year(münster,A?1970)(D.J.Evans and D.J Searles,2002). 2.3 Literature survey D uring the
first decade of the 20th century, the artificial synthesis of nitrates was being researched
because of fears that the word’s supply of fixed nitrogen was declining rapidly relative
to the demand(appl,M,1982)(Weinheim,Wiley.VCH,2006).

Nitrogen in its inactive, atmospheric gas form is very plentiful, but agriculturally useful
“fixed” nitrogen compounds were harder to come by at that time. Agricultural
operations require liberal amounts of fixed nitrogen compounds to produce good
yields(James?Laylin?K,1993). Haber discovered this high pressure synthesis of ammonia
in 1913 (Hager,Thomas,2008) The haber-bosch process provided a solution to the
shortage of fixed nitrogen. Using extremely high pressures(Hager,Thomas,2008). The
Haber process was created during the World War 1. It was brought up to help the
Germans since they were in need of nitrogen in order to make their various
explosives(Smil,Vaclav,2004).Since the roads were blocked by the Allies, they no longer
had their sources of nitrogen which were sodium nitrate and potassium
nitrate(Sitting,Marshal,1979).

The German chemist Fritz Haber then came up with a way to take nitrogen molecules
from the air to then be able to put it together with hydrogen in order to then be able to
form ammonia gas which is found to be the basic formula for the Haber
process(Haber,Fritz,1905). Fig-2.4(Flow sheet for production of ammonia by haber
process) 2.4 Manufacture of ammonia by Haber's synthesis method The he
primary arrange is refinement where pollutions, primarily sulfur compounds,
are expelled from the gas stream.(George T, Austain , 1984). Steam transforming is
performed in two stages. Within the essential arrange, the
endothermic responses take put at weights around 30 bar and temperatures of 800°C or
higher.

This is followed by an exothermic secondary reformer where air is added to the partially
reformed gas stream(Georage T, Austain, 1984). The carbon monoxide within
the gas clearing out the auxiliary reformer is converted to carbon dioxide within
the move reactors and after that expelled by scouring from the gas stream.
Any leftover carbon oxides are at that point changed over back to methane by
methanation some time recently compression of the hydrogen and nitrogen
to alkali union pressure.(Georage T , Austain ?1984) The final reaction stage is ammonia
synthesis where the hydrogen and nitrogen combine to form ammonia. This reaction
stage takes place at high pressure (100-350 bar) and is highly exothermic.[14].

This sponse may, (be) a reversible, (b) exothermic, and (c) continues with a diminish in
volume. Concurring to the Le Chatelier's guideline, 2.4.1 Desulphurization The
catalyst utilized within the steam changing prepare is exceedingly delicate to any Sulfur
compounds, therefore these compounds ought to be decreased to a concentration of
less than 0.15 mg/m3 bolster gas. To realize this, the bolster gas is preheated up to 350-
400 °C.

Thereafter, the sulfur compounds are hydrogenated to H2S, typically, using a cobalt
molybdenum catalyst, and then finally adsorbed on zinc oxide, In this way, the sulfur is
removed to less than 0.Ippm in the gas feed. R-SH+H2( H2S+ RH H2S+ZnO(ZnS+H2O
-The hydrogen required for the reaction is usually recycled from the synthesis section of
the plant. 2.4.2 Primary reforming Gas from the desulfurizer is sent to
the essential reformer for steam changing (ratio=steam/gas=3:1)
ential reformer comprises of a expansive number of high-nickel
chromium amalgam tubes filled with nickel transforming catalyst .Here superheated
steam is encouraged into the reformer with the methane. The
gas blend warmed with normal gas to 770C within the nearness of a nickel catalyst.At
this temperature the taking after harmony responses are driven, to changing over the
methane to hydrogen, carbon dioxide and little amounts of carbon monoxide: CH4
+H2O(3H2 +CO CH4+2H2O(4H2+CO2 CO+H2O(H2+ CO2 This vaporous blend is
known as amalgamation gas 2.4.3 Auxiliary transforming As it were 30-40% of the
hydrocarbon bolster is changed within the essential reformer since of the chemical
equilibria at the genuine working conditions . The temperature must be raised to
extend the transformation.

This is tired the auxiliary reformer by inside combustion of part of the gas with the
method air, which too provides the basic nitrogen for the ultimate union gas. The
method discuss is compressed to the changing weight and warmed encourage within
the primary reformer convection area to around 600 °C. The method gas is blended with
the discuss in a burner and after that passed over a nickel catalyst in auxiliary reformer.
The reformer outlet temperature is round 1,000 °C, and as much as 99% of the
hydrocarbon nourish (from the essential reformer) is changed over, giving
a leftover methane substance of .2-0.3% (dry gas base) within the prepare gas taking
off the auxiliary.

The reformer outlet temperature is around 1,000 °C, and up to 99% of the
hydrocarbon nourish (from the essential reformer) is changed over, giving
a remaining methane substance of .2-0.3% (dry gas base) within the handle gas clearing
out the secondary reformer. CO+ H2O(CO2+ H2 O2+2CH4 (2CO+ 4H2
O2+CH4(CO2+2H2 2O2+CH4 (2H2O+ CO2 The method gas is cooled to 350-400 °C in
a squander warm steam evaporator or boiler/super radiator downstream from
the auxiliary reformer.

As the catalyst that's utilized to create the alkali is immaculate press, water, carbon
dioxide and carbon monoxide must be expelled from the gas stream to avoid oxidation
of the press. carried out within the next three steps. 2.4.4. Shift conversion The
method gas from the auxiliary reformer contains 12-15% CO (dry gas base) and most of
the CO is changed over within the move segment agreeing to the response. CO
+H2O(CO2+ H2 In the High Temperature Shift (HTS) conversion, the gas is passed
through a bed of iron oxide/chromium oxide catalyst at around 400 °C, where the CO
content is reduced to about3% (dry gas base), constrained by the move harmony at
the genuine working temperature. There's a inclination to utilize copper containing
catalyst for expanded transformation. The gas from the HTS is cooled and passed
through the Moo Temperature Move (LTS) converter. This LTS converter is filled with a
copper oxide/zinc Oxide-based catalyst and works at almost 200-220 °C.

The residual CO substance within the changed over gas is around 0.2-0.4% (dry gas
base. A low residual CÕ content is important for the efficiency of the process.
Condensate: the method gas from the moo temperature move converter contains
mainly H2, N2, CO2, and the excess process steam. The gas is cooled and most of
the overabundance steam is condensed some time recently it enters the CO2, removal
system .This condensate ordinarily contains 1,500-2,000 ppm of alkali 800-1,200 ppm of
methanol. Minor sums of amines, formic corrosive and acidic corrosive can
be show within the condensate.

All these components should be stripped from the condensate and recycled in
processes. 2.4.5. CO2 removal This handle step evacuates the CO2 from the response
gas.The CO2 is evacuated in a physical retention handle. The solvents utilized in
chemical assimilation forms are basically fluid amine arrangements, e.g. mono
ethanolamine (MEA) enacted methyl diethanolamine (MDEA) or potassium
carbonate arrangements.. Two ordinarily utilized physical assimilation solvents are glycol
dimethylethers and propylene carbonate which diminishes the substance down
to approximately 50ppm. 2.4.6.Methanation The little sums of CO and CO2
remaining within the union gas, are noxious for the smelling salts blend catalyst and
must be expelled by transformation to CH, in the methanator.

CO+3H(CH4+H2O CO2+ 4H2(CH4+2H2O The responses take put at around 300 °C in a

reactor filled with a nickel containing catalyst. Methane is not involved in the synthesis
reaction, but the water must be removed before entering the converter. This is done
firstly by cooling followed by condensation downstream ofthe methanator. 2.4.7.
Compression Modern ammonia plants use centrifugal compressors to pressurize the
synthesis gas to the required level (100-250 bar, 350-550 °C) for ammonia synthesis.
Molecular sieves are sometimes used after the first compressor stage to remove the last
traces of H2O,CO and CO2 from the synthesis gas. These compressors are usually driven
by steam turbines, utilizing steam produced from the excess process heat. 2.4.8

NH3 synthesis The union of smelling salts takes put on an press catalyst at weight more
often than not within the extend of 100-250 bar and at temperatures of between 350
and 550 °C. N2+3H2(NH3 Only 10-20 % % of the blend gas is changed over per pass
to alkali, due to unfavorable harmony conditions. The unreacted gas
is reused after expelling the smelling salts shaped and New blend gas is
supplemented within the circle. As the exothermic
synthesis response continues, there's a decrease in volume and so the next pressure and
lower temperature favors the response. Routine transforming with methanation as the
ultimate decontamination step produces a union gas containing unreacted gasses and
inerts (methane and argon). In arrange to avoid the aggregation of these inerts,
a nonstop cleanse gas stream should be connected..

Purge gas fundamentally contains smelling salts, nitrogen, hydrogen, inerts and
unreacted gasses. The estimate of this cleanse stream controls the level of inerts within
the circle, keeping these to around 10- 15 %. The purge gas is cleaned with water
to evacuate, before then being used as fuel or before being sent for hydrogen
recovery.[15] Fig-3.1 (Flow sheet for production of ammonia by haber process)

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