Production of Sulfuric Acid PDF
Production of Sulfuric Acid PDF
By
Ahmed Hasan M. Ali
Supervisor:
Assist. Prof. Dr. Ahmed D. Wehaib
April 2016
1
Chapter One
Introduction
1.1 Introduction
Sulfuric acid : sulfuric acid is a chemical compound , colorless , odorless
, extremely , oily liquid and highly corrosive strong mineral acid with the
molecular formula H₂SO₄ and molecular weight 98.079 g/mol . which is
soluble in water at all concentrations and sometimes called oil of vitriol.
History :
Sulfuric acid has been an important item of commerce since the early to
middle 1700 s . It has been known and used since the Middle Ages . In
the eighteenth and nineteenth centuries it was produced almost entirely by
the chamber process in which oxides of nitrogen (as nitrosyl compounds)
are used as homogeneous catalysts for the oxidation of sulfur dioxide .
The product made by this process is of rather low concentration (77-78 wt
% H₂S0₄) . This is not high enough for many of the commercial uses of
the 1990 s . The chamber process is therefore considered obsolete for
primary sulfuric acid production . However, more recently modifications
to the chamber process have been used to produce sulfuric acid from
metallurgical off-gases in several European plants . During the first part
of the twentieth century , the chamber process was gradually replaced by
the contact process . The primary impetus for development of the contact
process came from a need for high strength acid and oleum to make
synthetic dyes and organic chemicals . The contact process employing
platinum catalysts began to be used on a large scale late in the nineteenth
century. The pace of its development was accelerated during World War I
in order to provide concentrated mixtures of sulfuric and nitric acid for
explosives production . In 1875 a paper by Winkler awakened interest in
2
the contact process first patented in 1831. Winkler claimed that
successful conversion of SO₂ to SO3 could only be achieved with
stoichiometric undiluted ratios of SO₂ and O₂ . Although erroneous this
belief was widely accepted for more than 20 years and was employed by
a number of firms . Meanwhile other German firms expended a
tremendous amount of time and money on research . This culminated in
1901 with Knietsch's lecture before the German Chemical Society
revealing some of the investigations carried out by the Badische Anilin-
und-Soda-Fabrik . This revealed the abandonment of Winkler's theory
and further described principles necessary for successful application of
the contact process . in 1915 an effective vanadium catalyst for the
contact process was developed and used by Badische in Germany .
This type of catalyst was employed in the United States starting in 1926
and gradually replaced platinum catalysts over the next few decades .
Vanadium catalysts have the advantages of exhibiting superior resistance
to poisoning and being relatively abundant and inexpensive compared to
platinum . After World War II , the typical size of individual contact
plants increased dramatically in the United States and around the world in
order to supply the rapidly increasing demands of the phosphate fertilizer
industry . The largest sulfur burning plants as of the mid-1990 s produce
approximately 3300 metric tons of acid per day . Plants using sulfur in
other forms especially SO₂ from smelting operations (metallurgical
plants) have also increased in size . One metallurgical plant has been built
to produce 3500 metric tons of acid per day . Another significant change
in the contact process occurred in 1963 , when Bayer AG announced the
first large-scale use of the double-contact (double-absorption) process . In
this process SO₂ gas that has been partially converted to SO 3 by catalysis
is cooled passed through sulfuric acid to remove SO 3 reheated , and then
3
passed through another one or two catalyst beds . Through these means,
overall conversions can be increased from about 98% to 99.7% , there by
reducing emissions of unconverted SO₂ to the atmosphere . Because of
world wide pressures to reduce SO₂ emissions , most plants as of the mid
— 1990 s utilize double-absorption . An early U.S . patent disclosed the
general concept of this process but apparently was not reduced to practice
at that time .
1 - Production Fertilizer
4 - Making Detergents
5 - A Dehydrating agent.
7- A Catalyst .
4
1.2 Physical properties of sulfuric acid:
There are many fingers shows the gravity with concentration , viscosity
with concentration , boiling points with concentrations and other bellow :
5
6
1.3 Chemical Properties Of H2SO4 :
Sulfuric acid is a di basic acid i-e when dissolved in water one molecule
produces two hydrogen atoms.
H2SO4 2H + SO4
7
Hot and concentrated acid gives SO2, with metals like Cu, Hg, Ag and Pb
…. Etc.
II - it oxidizes " HI " and " HBY " to iodien " I " and bramine " Br 2"
HI + H2SO4 I2 + SO2 + H2O
HBr + H2So4 Br2 + SO2 + H2O
8
1.3.7 Drying and Dehydration Agent
C12H22O11 C + 11 H2O
HCOOH CO + H2O
9
1.4 Methods of Production :
There are two major processes for production of sulfuric acid ( H2SO4 ) :-
1-lead chambers
2-contact process
this processes available commercially.
11
1.4.2 Contact process :
This method discovered the first one in 1831 by Englishman his name
Phillips included his patent the basic features for modern contact
process , even in 1900, it has not built a factory in a manner of contact
in the United States , even though this method has gained importance in
Europe duties by the urgent need for Oleum and acid with high
concentration for slfonation and especially in the manufacture of dyes .
And the basic principle of the process begin by burning sulfur with an
abundance of air to produce sulfur dioxide ( SO2 ) the increase in
oxygen useful to the contact process because it make the process more
efficient. In both processes ( contact process and lead chambers ) sulfur
dioxide (SO₂) is oxidized to sulfur trioxide ( SO3 ) . The sulfur dioxide
12
is obtained by burning sulfur by burning pyrites ( iron sulfides ) by
roasting nonferrous sulfide ores preparatory to smelting , or by burning
hydrogen sulfide gas H₂S . Then in contact process convert sulfur
dioxide ( SO₂ ) to sulfur trioxide ( SO3 ) with vanadium oxide V₂O5 as a
catalyst which is in the form of tiny cylinders packaged the reaction
tower . In the final stage , sulfur trioxide is converted to sulfuric acid .
The sulfur trioxide gas is absorbed into very concentrated sulfuric acid (
a 98 per cent solution of H₂SO₄ in water ) , producing a thick fuming
liquid called oleum . The oleum is mixed carefully with water , and the
sulfuric trioxide in the oleum reacts with the water to formed sulfuric
acid with 98% concentration as follows :
13
Chapter Two
Material And Energy Balance
14
SO3 (g) + H2O (L) H2SO4 (L)
Then, SO3 required = 4.166 kmole
Also its assumed that the overall conversion of SO 2 to SO3 in the reactor
is 99.8%
SO2 (g) + 1⁄2 O2 (g) SO3 (g)
Then SO2 required = 4.166 / 0.998 = 4.174 kmole
Assuming 100% combustion of Sulfur ,
S(L) + O2 (g) SO2 (g)
Then S required = 4.174 kmole = 133.568 kg ( liquid )
Amount of oxygen required to convert ( 1 ) kmole of S to SO 3
= 1.5 kmole according to the equations below :
S(L) + O2 (g) SO2 (g) 1 kmole of O2 1.5 kmole
SO2 (g) + 1⁄2 O2 (g) SO3 (g) 0.5 kmole of O2
Then, amount of Oxygen required = 4.174 x 1.5 = 6.261 kmole
As cited in the literature that some amount of excess oxygen must be used
Using 20% excess
O2 required to process = 6.261 * 1.2 = 7.5132 kmole
From this, the total dry air that is coming in can be calculated as :
Air O2
100 21
X 7.5132
X = (7.5132* 100)/ 21 = 35.777 kmole of Dry air inlet to process
= 35.777 * 29 = 1037.533 kg
Q = 1036.421 kg
15
Sulfur burner :
The combustion reaction takes place inside the burner where Sulfur is
oxidized to Sulfur Dioxide .
Dry air entering to burner = 1037.533 kg / 29 ( kg / kmole )
= 35.777 kmole
Sulfur entering ( S ) = 4.174 kmole
Oxygen entering O2 = 7.5132 kmole
16
Comp. equipment Stream m ( Kg ) no. moles ( Kmole )
S Burner 1 133.568 4.174
O2 Burner 2 240.4224 7.5132
Reactor :
O2 entering reactor = 3.339 kmole
N2 entering reactor = 28.263 kmole
SO2 entering reactor = 4.174 kmole
SO3 entering reactor = 0.0 kmole
In the reactor the reaction below is take place :
SO2 (g) + 1⁄2 O2 (g) SO3 (g
From chemical equation above we can find O2 required for this reaction :
SO2 O2
1 0.5
4.174 X
X = 2.087 kmole of O2 required for the reaction
O2 leaving the reactor = 3.339 – 2.087 = 1.252 kmole
N2 leaving the reactor = 28.263 kmole
SO2 leaving the reactor = 4.174 * 0.002 = 0.008 kmole
SO3 leaving the reactor = 4.174 * 0.998 = 4.166 kmole
17
Comp. equipment stream m ( Kg ) no. moles ( Kmole ) state
SO2 converter 3 267.136 4.174 In to stage 1
O2 converter 3 106.848 3.339 In to stage 1
N2 converter 3 395.682 28.263 In to stage 1
SO2 converter 4 69.45536 1.08524 In to stage 2
O2 converter 4 57.42784 1.79462 In to stage 2
N2 converter 4 395.682 28.263 In to stage 2
SO3 gen. converter 4 247.1008 3.08876 In to stage 2
SO3 total converter 4 247.1008 3.08876 In to stage 2
SO2 converter 5 20.30234 0.317224 In to stage 3
O2 converter 5 45.13958 1.410612 In to stage 3
N2 converter 5 395.682 28.263 In to stage 3
SO3 gen. converter 5 61.44128 0.768016 In to stage 3
SO3 total converter 5 308.5421 3.856776 In to stage 3
SO2 converter 6 8.815488 0.137742 In to stage 4
O2 converter 6 42.26787 1.320871 In to stage 4
N2 converter 6 395.682 28.263 In to stage 4
SO3 gen. converter 6 14.35856 0.179482 In to stage 4
SO3 total converter 6 322.9006 4.036258 In to stage 4
SO2 converter 7 0.512 0.008 Out from stage 4
O2 converter 7 42.13987 1.316871 Out from stage 4
N2 converter 7 395.682 28.263 Out from stage 4
SO3 gen. converter 7 10.35152 0.129394 Out from stage 4
SO3 total converter 7 333.2522 4.165652 Out from stage 4
18
Absorber tower :
In absorber tower the sulfur trioxide ( SO 3 ) absorbed by sulfuric
acid with purity 98% and leaving the as a product with purity 100% but
we Must be cooled to avoid disintegration the acid to SO 3 gas and water
in acid boiling point . also mentioned in the literature that “ its required to
take the strength of the solvent H2SO4 for absorption of SO 3 not to increase
by more than1 – 2 % and the best absorption will occur when the
absorbing acid has the strength between the range 97.5 to 99 % ” .
SO3 (g) + H2O (L) H2SO4 (L)
From chemical equation above we can find H2O required for this reaction
:
SO3 H2O H2SO4
1 1 1
4.166 4.166 4.166
H2O = 4.166 kmole required for the reaction to produce H2SO4
19
Comp. equipment Stream m ( Kg ) no. moles ( Kmole )
SO2 absorber 7 0.512 0.008
O2 absorber 7 40.064 1.252
N2 absorber 7 395.682 28.263
SO3 absorber 7 333.28 4.166
H2SO4 absorber 8 20413.4 208.3
20
Diluter :
21
2.2 Energy balance :
Burner :
∆H in = m cp ∆T
25
∆H O2 , N2 , S = m ∫115 𝑎 + 𝑏𝑇 + 𝑐𝑇 + 𝑐𝑇 dT
1100
∆H O2 , N2 , SO2 = m ∫25 𝑎 + 𝑏𝑇 + 𝑐𝑇 + 𝑐𝑇 dT
We can solve the equation above by using Excel application to make the
calculation easier , we ginned the resultant show in table below :
22
Heat Exchanger A :
1100
In : ∆H O2 , N2 , SO2 = m ∫25 𝑎 + 𝑏𝑇 + 𝑐𝑇 + 𝑐𝑇 dT
410
Out : ∆H O2 , N2 , SO2 = m ∫25 𝑎 + 𝑏𝑇 + 𝑐𝑇 + 𝑐𝑇 dT
65
∆H H2O = m ∫25 𝑎 + 𝑏𝑇 + 𝑐𝑇 + 𝑐𝑇 dT
23
Reactor Stage 1 :
∆H in + ∆Hr = ∆H out
25
In : ∆H O2 , N2 , SO2 = m ∫410 𝑎 + 𝑏𝑇 + 𝑐𝑇 + 𝑐𝑇 dT
1100
Out : ∆H O2 , N2 , SO3 = m ∫25 𝑎 + 𝑏𝑇 + 𝑐𝑇 + 𝑐𝑇 dT
Heat Exchanger 1 :
601
In : ∆H O2 , N2 , SO2 = m ∫25 𝑎 + 𝑏𝑇 + 𝑐𝑇 + 𝑐𝑇 dT
24
438
Out : ∆H O2 , N2 , SO3 = m ∫25 𝑎 + 𝑏𝑇 + 𝑐𝑇 + 𝑐𝑇 dT
65
∆H H2O = m ∫25 𝑎 + 𝑏𝑇 + 𝑐𝑇 + 𝑐𝑇 dT
Reactor Stage 2
∆H in + ∆Hr = ∆H out
25
In : ∆H O2 , N2 , SO2 = m ∫438 𝑎 + 𝑏𝑇 + 𝑐𝑇 + 𝑐𝑇 dT
485
Out : ∆H O2 , N2 , SO3 = m ∫25 𝑎 + 𝑏𝑇 + 𝑐𝑇 + 𝑐𝑇 dT
25
Heat Exchanger 2 :
485
In : ∆H O2 , N2 , SO2 = m ∫25 𝑎 + 𝑏𝑇 + 𝑐𝑇 + 𝑐𝑇 dT
432
Out : ∆H O2 , N2 , SO3 = m ∫25 𝑎 + 𝑏𝑇 + 𝑐𝑇 + 𝑐𝑇 dT
65
∆H H2O = m ∫25 𝑎 + 𝑏𝑇 + 𝑐𝑇 + 𝑐𝑇 dT
Reactor Stage 3 :
∆H in + ∆Hr = ∆H out
25
In : ∆H O2 , N2 , SO2 = m ∫432 𝑎 + 𝑏𝑇 + 𝑐𝑇 + 𝑐𝑇 dT
26
444
Out : ∆H O2 , N2 , SO3 = m ∫25 𝑎 + 𝑏𝑇 + 𝑐𝑇 + 𝑐𝑇 dT
Heat Exchanger 3 :
444
In : ∆H O2 , N2 , SO2 = m ∫25 𝑎 + 𝑏𝑇 + 𝑐𝑇 + 𝑐𝑇 dT
427
Out : ∆H O2 , N2 , SO3 = m ∫25 𝑎 + 𝑏𝑇 + 𝑐𝑇 + 𝑐𝑇 dT
65
∆H H2O = m ∫25 𝑎 + 𝑏𝑇 + 𝑐𝑇 + 𝑐𝑇 dT
27
Reactor Stage 4 :
∆H in + ∆Hr = ∆H out
25
In : ∆H O2 , N2 , SO2 = m ∫427 𝑎 + 𝑏𝑇 + 𝑐𝑇 + 𝑐𝑇 dT
430
Out : ∆H O2 , N2 , SO3 = m ∫25 𝑎 + 𝑏𝑇 + 𝑐𝑇 + 𝑐𝑇 dT
28
Heat Exchanger 4 :
430
In : ∆H O2 , N2 , SO2 = m ∫25 𝑎 + 𝑏𝑇 + 𝑐𝑇 + 𝑐𝑇 dT
427
Out : ∆H O2 , N2 , SO3 = m ∫25 𝑎 + 𝑏𝑇 + 𝑐𝑇 + 𝑐𝑇 dT
65
∆H H2O = m ∫25 𝑎 + 𝑏𝑇 + 𝑐𝑇 + 𝑐𝑇 dT
Chapter Three
Equipment Design
29
Tube Side ( Gases : SO2 & O2 & N2 )
t 1 = 1100 ◦ C
t 2 = 410 ◦ C
T1 = 25 ◦ C
T2 = 65 ◦ C
Q = UA ∆Tlm Ft
Where
30
Ft = Temperature correction factor
𝐾𝐽 1000𝐽 ℎ
Q = = 32857827.27 * * *
ℎ𝑟 𝐾𝐽 3600𝑆
Q = 9127174.42 W
(25−410)−(65−1100)
∆Tlm = 25−410
ln( )
65−1100
∆Tlm = 658
𝑇1−𝑇2
R=
𝑡2−𝑡1
25−65
R= = 0.057
410−1100
𝑡2−𝑡1
S=
𝑇1−𝑡1
410−1100
S= = 0.64
25−1100
Or from equation :
31
[3]
(1−0.64)
√(0.0032+1) ln[(1−0.057∗0.64)]
Ft = = 0.998 ≈ 1
2−0.64[0.057+1−√(0.0032+1 )
(0.057−1)ln[ ]
2−0.64[0.057+1+√(0.0032+1 )
U = 80 – 250
𝑄 9127174.42
A= = = 156 m2
𝑈∆𝑇𝑙𝑚 𝐹 90∗658 ∗1
Select
di = do – 2*3.2
= ᴫ *0.05 * 1.83
= 0.287 m2
32
𝑇𝑜𝑡𝑎𝑙𝑎𝑟𝑒𝑎
No. Of tube =
𝑎𝑟𝑒𝑎𝑜𝑓𝑜𝑛𝑒𝑡𝑢𝑏𝑒
156
Nt = = 544
0.287
𝑡1 −𝑡2
Mean tube temperater tm =
2
1100+410
= = 755 ◦ C = 1023 K
2
𝑃𝑀
𝜌v = 𝑅𝑇
T = 755 ◦ C = 1023 K
1000∗124
𝜌v = = 14.57928 Kg/m3
8.314∗1023
Cp = 3.077 KJ/Kg.C
K = 0. 54 w/m.c [4]
𝜇 = 0.1 centipoise
= 1*10-4 Ns/m2
544
No. of tube per pass = = 272
2
1164.5
Mass flow rate per tube m =
272∗3600
m = 0.00118 Kg/s
33
M = 𝜌 u A
Where
𝒎 𝟎.𝟎𝟎𝟏𝟏𝟖
u= = = 23.5 m/s
𝝆𝑨 𝟏𝟒.𝟓𝟕∗𝟎.𝟏𝟒𝟗∗𝟏𝟎 −𝟒
𝜇
Nu = 0.021 Re0.8 Pr0.33( )0.14 [3]
𝜇𝑤
ℎ𝑖𝑑
𝑖
Nu = Nusselt number =
𝑘
𝑐𝑝𝜇
Pr = prondtl number =
𝑘
34
u = fluid velocity m/s
Re = 3481
𝜇
( )0.14 = 1 [3]
𝜇𝑤
Nu =0.021(3481)0.8 (0.00064)0.33(1)0.14
Nu = 0.266
ℎ𝑖 𝑑𝑖 ℎ𝑖 ∗0.00436
Nu = = 0.258 =
𝑘 0.54
hi = 3295.6 w/m2.◦c
𝑇1 +𝑇2
Mean shell temperature Tm =
2
25+65
Tm = = 45◦ C
2
𝜌 = 990 kg/m3
𝜇 = 0.595 mP.s
Cp = 4.18 kJ/kg.◦ C
K = 0.627 w/m.◦ C
35
𝜇
Nu = JnRe Pr0.33( )0.14 [3]
𝜇𝑤
Where
ℎ𝑜 𝑑 𝑒
Nu = Nusselt number =
𝑘
𝜌𝑢𝑠 𝑑𝑒
Re = Reynolds number =
𝜇
𝑐𝑝𝜇
Pr = Prandtl number =
𝑘
de = equivalent diameter m
1.27
de = (pt2 – 0.785 do2) [3]
𝑑𝑜
Where
do, de and pt in mm
do = 50mm
Pt = 1.25(50) = 62.5mm
36
1.27
de = (62.52 – 0.785*502) = 49.4mm
50
= 0.0494m
𝑁𝑡
Db = do( )1/n1 [3]
𝑘1
Where
Db = bundle diameter mm
K1 and n1 = constant
K1 =0.156
544 1/2.291
Db = 50( ) = 1758 mm
0.156
Ds – Db = 60 mm Fig 12.10
𝑝𝑡 −𝑑𝑜
As =( )(Ds*𝑙𝐵 ) [3]
𝑝𝑡
Where
lB = baffle Spacing m
37
lB = 0.5Ds
62.5−50
AS = (1.818 ∗ 0.909) = 0.33 m2
62.5
𝑤𝑠
Gs =
𝐴𝑠
Where
Ws = 10909.5 kg/h
= 3.03 kg/s
3.03
Gs = = 9.16 kg/m2.s
0.33
𝐺𝑠 9.16
GS = ps us us = = = 0.0092 m/s
𝜌𝑠 990
𝐺𝑠 𝑑𝑒 9.16∗0.0494
Re = = = 1189
𝜇 5.9∗10−4
Nu =5*10-3(1189)(3.39)0.33 (1)
Nu = 75.36
ℎ𝑜 𝑑𝑟
Nu =
𝜇
38
ℎ𝑜 ∗0.0494
75.36 =
0.627
ho = 956.6 w/m2.c
1 1 1 𝑑𝑜 ln 𝑑𝑜 /𝑑𝑖 𝑑𝑜 1 𝑑𝑜 1
= + + + . + . [3]
𝑈° ℎ𝑜 ℎ𝑜 𝑑 2𝑘𝑤 𝑑𝑖 ℎ𝑖𝑑 𝑑𝑖 ℎ𝑖
Where
hid = 3000
U◦ = 87w/m2.c
U◦ ass = 90w/m2c
Assume U = 87 W/m2.◦ c
39
9127174.42
A= = 161.5 m2
87∗288.9∗1
161.5
Nt = = 562
0.287
562
No.of tube per pass = = 281
2
1164.5
Mass flow rate per tube =
281∗3600
𝑚 = 0.00115𝑘𝑔/𝑠
0.00115
u= =22.7 m/s
14.57∗0.149∗10−4
3.39∗22.7∗0.00436
Re = = 3365
1∗10−4
Nu = 0.021 (3365)0.8(0.0064)0.33(1)
Nu = 0.258
ℎ𝑖 ∗0.00436
0.258= hi = 3207 w/m. ◦ c
0.54
562
Db = 50( )1/2.291 = 1784 mm
0.156)
Ds – Db = 58 Ds = 1844 mm [3]
= 1.844 m
40
lb = 0.5(1.884) = 0.992 m2
62.5−50
As =( )(1.884*0.922) = 0.34 m2
62.5
7.374
Gs = = 8.9 kg/m2.s
0.0324
990∗22.7∗0.0494
Re = =2387
5.9∗10−3
Nu = 5*10-3(1508)(3.03)0.33(1)
Nu = 132.51
ho ∗0.0494 ◦
132.51 = h0 = 992.6 w/m2. C
0.627
U◦ = 86 w/m2. ◦c
Uass = 87 w/m2.◦c
87−86
Error = *100 % = 1%
87
41
Tube side pressure drop
𝑙 𝜇 𝜌𝑢2
Δpt = NP[8 jf ( )( )−0.14 +2.5][ 𝑡
] [3]
𝑑 𝑖 𝜇𝑊 2
Where
jf = friction factor
for Re = 1508
1.84 3.39∗22.72
Δpt = 2[8 *2.9*10 -3 ( ) (1)-0.14 +2.5][ ] [3]
0.00436 2
= 6068 N/m2
= 6.068 kpa
𝐷 𝑙 𝜇 𝜌𝑢2
Δpt = 8 jf ( 𝑆 ) ( )( )−0.14 [ 𝑡
] [3]
𝑑𝑒 𝑙𝐵 𝜇𝑊 2
Where
= 987 N/m2
Pipe sizing
Where
𝜌 = 3.39 kg/m3
𝜌 = 990 kg/m3
43
3.2 Design Reactor
Catalyst :
Properties:
44
The volume can be evaluated using method as SIMPSONS one –third
Rule :
𝑋 𝐹𝐴˚
V =∫0 dx = h/3 {f(x)0 + 4f(x)1 + f(x)2}
−𝑟𝐴
H = X2 – X0
-rA = Kca
K2 = K2˚exp – E/RT
E2 = 47,400 kcal/kgmol
= 0.02934 Kmol/m3.h
= 0. 547 Kmol/m3.h
4.174
𝑦𝐴 ° = = 0.12
35.746
ɛA = yA˚ϐ
−1
𝜖𝐴 = ( ) (0.12) = −0.12
1
CA˚= yA*˚p/RT˚
Simpsons rule:
X ( 1–x)/(1+ƹx) (1+x)/(1–x)=f(x)
0 1 1
0.196 0.82336 1.487
0.329 0.638012 2.28
0.588 0.4432 3.584
0.784 0.2384 8.2592
0.98 0.02266 99
H = 0.196
= 8.4817
V = 43.46 m3
𝜋
V = *D2*L
4
𝜋
43.46 = *D2*(4D)
4
D = 2.399 m
= 9.596 m
46
Volume of catalyst in 1st bed = 43.46/4
= 10.8
= 46861 kg
= 1.899 m
= 123.6 Kg/m2
= 4 494 Kgf/cm2
47
K = 1.0337
D˚= K Di
D˚=1.0337*2.339
D˚=2.478m
= 69 mm
Temperature : 683-874 k˚
Volume : 43.46 m3
48
3.3 Design of Absorber
Inlet gas
49
Column diameter
𝐿 𝜌
F L.V = ( )( 𝑉 )0.5
𝐺 𝜌𝐿
Where :
vapor density
𝑃𝑀𝑎𝑣
ρ V=
𝑅𝑇
M a v = Σ Mi y i
Where :
M a v = (80*1)
= 80 kg/kmol
T = 30 ◦ C = 303 K
100∗80
ρ V= = 3.17 kg/m3
8.314∗303
50
Liquid density :
Density of H2O at 30 ◦ C
ρ L =1000 kg/m3
L = 74.988 kg/hr
L = 0.0208 kg/s
G = 333.28 kg/hr
G = 0.0926 kg/s
Where:
VW* = gas mass flow rate per unit cross – sectional area kg/m2.s
K4 = constant
Fp = packing factor .
Design pressure drop for absorber from from15 to50 mmH2O /m packing
K4 = 3 fig 11.44
K4 at flooding = 7
51
𝐾4
Percent flooding = ( )0.5* 100%
𝐾4 𝑎𝑡𝑓𝑙𝑜𝑜𝑑𝑖𝑛𝑔
3
= ( )0.5 *100% = 70%
6
Viscosity of H2O at 30 ◦ C
3∗3.17(1000−3.17)
VW* = [ ]0.5 [3]
0.722∗10−3 0.1
13.1∗170( )
1000
= 4.22 kg/m2.s
𝐺
A= ∗
𝑉𝑊
Where :
0.0926
A=( 4.22
) = 3.4 m2
𝜋
A= D2
4
𝜋
3.4 = D2 D = 1.7 m
4
Height of column :
Z = HOG . NOG
Where :
Z = height of packing m.
52
HOG = over all height of gas phase transfer unit m.
𝑚𝐺
HOG = Hg + HL
𝐿
Where :
PA◦ = 0
PA* = PA◦ XA
𝑃𝐴∗ 𝑃𝐴°
= XA
𝑃𝑇 𝑃𝑇
𝑃°
y*A = m xA m = ( 𝐴) = 0
𝑃𝑇
m = ρV u A
𝑚
u=
𝐴𝜌𝑉
0.0926
u=
0.022∗3.17
= 13.5 m/s
53
For u = 13.5 m/s , 1.5 inch intalox saddle 1 bar and 30 ◦ C
Hg = 2 m
𝑦 𝑑𝑦
NOG =∫𝑦 1
2 𝑦−𝑦 ∗
𝑦 𝑑𝑦 𝑦1
NOG= ∫𝑦 1 = Ln
2 𝑦 𝑦2
y1 = 0.01
y2 = 0.0005
0.01
NOG = Ln = 2.99
0.0005
Z = (0. 5) (2.99)
= 4.8 m
Type Packed
Length packed 4.8 m
Diameter 1.7 m
𝜋
Volume = D2L 0.0471
4
Temp. ◦ C 30 ◦ C
Pressure bar 1bar
Material of count Carbon steel
Chapter Four
54
Process Control
4.1 Introduction
The equipment is used in the control and measurement have a significant
role in the control of the process as well as to minimize losses and to
prevent damage and reduce risk. There are no industrial process devoid of
control and measurement, because these are very important services in
each process even if it was simple. Typically in each unit in the lab, there
is a room called the control room that contains the hardware control
associated with the equipment and machines for the process of production
and the panel representing each unit, the index for each device and the
lamps and measuring devices can be of this room control of each device
and can stop the process in case there index to a significant error such as
an explosion or fire.
55
E = TR – TM
And trying to control device to reduce the amount of error to less close to
zero.
1- proportional control.
2- proportional integral.
3- proportional derivative.
4- PIB.
56
4- process: the process is to be controlled, such as flow, pressure or
temperature of the process … etc.
Set point
controller Final process E RSP
control
Rm Measuring controlled
element
57
4.3 control on reactor :
58
Chapter Five
Location , Economic and Safety Consideration
59
5.1.1: H2SO4 Plant Location
Based on these previous factors which are required in H2SO4
manufacturing plant, we select ( Al-Ramadi /Al-Mohammadiat /
industrial city Alkilo 70 ) Sulfur can be obtained from ( Al-Mishraq
Sulphur State Company ) .
The location of the plant can have a crucial effect on the profitability of a
project, and the scope for future expansion. Many factors must be
considered when selecting a suitable site, the principle factors to consider
are:
1- Marketing area :
For materials that are produced in bulk quantities; such as cement,
mineral acids, and fertilizers, where the cost of the product per tone is
relatively low and the cost of transport a significant fraction of the sales
price, the plant should be located close to the primary market. This
60
consideration will be less important for low volume production, high-
priced products; such as pharmaceuticals.
2- Raw materials
The availability and price of suitable raw materials will often determine
the site location. Plants producing bulk chemicals are best located close to
the source of the major raw material; where this is also close to the
marketing area.
3- Transport
The transport of materials and products to and from the plant will be an
overriding consideration in site selection.
4- Availability of labor
Labor will be needed for construction of the plant and its operation.
Skilled tradesmen will be needed for plant maintenance.
5- Utilities (services)
Chemical processes invariably require large quantities of water for
cooling and general process use, and the plant must be located near a
source of water of suitable quality. Process water may be drawn from a
river, from wells, or purchased from a local authority.
6- Environmental impact and effluent disposal
All industrial processes produce waste products, and full consideration
must be given to the difficulties and cost of their disposal. An
environmental impact assessment should be made for each new project,
or major medication or addition to an existing process.
7- Land (site considerations)
Sufficient suitable land must be available for the proposed plant and for
future expansion. The land should ideally be flat, well drained and have
suitable load-bearing characteristics.
8- Climate
61
Adverse climatic conditions at a site will increase costs. Abnormally low
temperatures will require the provision of additional insulation and
special heating for equipment and pipe runs. Stronger structures will be
needed at locations subject to high winds (cyclone/hurricane areas) or
earthquakes.
62
6. Any other nuisances.
7. The environmental friendliness of the products.
Waste management: Waste arises mainly as byproducts or unused
reactants from the process, or as off-specification product produced
through mis-operation. The designer must consider all possible sources
of pollution and, where practicable, select processes that will eliminate or
minimize waste generation. Unused reactants can be recycled and off-
specification product reprocessed. Integrated processes can be selected:
the waste from one process becoming the raw material for another. When
waste is produced, processes must be incorporated in the design for its
treatment and safe disposal. The following techniques can be considered :
1. Dilution and dispersion.
2. Discharge to foul water sewer (with the agreement of the appropriate
authority).
3. Physical treatments: scrubbing, settling, absorption and adsorption.
4. Chemical treatment: precipitation (for example, of heavy metals),
neutralization.
5. Biological treatment: activated sludge and other processes.
6. Incineration on land, or at sea.
7. Landfill at controlled sites.
8. Sea dumping (now subject to tight international control).
Noise: Noise can cause a serious nuisance in the neighborhood of a
process plant. Care needs to be taken when selecting and specifying
equipment such as compressors, air-cooler fans, induced and forced
draught fans for furnaces, and other noisy plant. Excessive noise can also
be generated when venting through steam and other relief valves, and
from flare stacks. Such equipment should be fitted with silencers.
63
5.5 Cost Estimation :
Pressure 𝑃 = 10𝑏𝑎𝑟
Cost = 20000$
Material factor =1
64
5.5.2 Cost Estimation on reactor
Height ℎ = 9.596𝑚
Diameter 𝐷 = 2.399𝑚
Pressure P= 10 bar
Cost=2500$
Material factor =2
Height ℎ = 4.8𝑚
Diameter 𝐷 = 1.7𝑚
65
Pressure 𝑃 = 10𝑏𝑎𝑟
Cost=5500$
Material factor =1
Chapter Six
Conclusion and Recommendation
6.1 Conclusions
The case study of the manufacture of sulfuric acid emphasizes the
benefits of a systematic design based on the analysis of the
reactor/condenser/absorber . The core of the process is the chemical
reactor, and in which the reaction is take place ( convert sulfur dioxide to
sulfur trioxide ) on a vanadium oxide V₂O5 as a catalyst, as well as the
safety and technological constraints. In this process "Accidental
66
pollution" there is always a risk of accidental pollution when chemicals
are produced and handled. The more common a chemical, the more
information is available about the different hazards and the lower the risk
of accidental pollution. The highest risk for accidental pollution is during
the transportation of the product . There is also a risk of pollution from
the storage of sulfuric acid and different plants have different systems to
collect leaks and spillages depending on guidelines for the storage of
acid. Gas leaks are not normally a problem as they are handled by various
monitoring and control systems, which measure the SO2 content in the
air.
6.2 Recommendation
Concern about the toxicity of sulfuric acid in the workplace atmosphere is
focused on its potential, as an inhaled aerosol, to exert local effects on the
respiratory tract, as a consequence of low pH. Such effects can be
manifested as sensory irritation of nerve endings, acute or longer term
inflammation at various sites along the length of the respiratory tract
epithelium, and ultimately the possibility of tumor formation in the
respiratory tract, believed to be a consequence of sustained tissue
inflammation and repair processes. Human carcinogenicity data and the
findings of a recent 28-day inhalation study in rats suggest that the larynx
is a site of particular concern, in relation to epithelial inflammation,
damage and ultimately cancer.
67
The identification of a clear NOAEL for this range of potential
respiratory tract effects is difficult, from the available data. However, the
recent 28-day inhalation study in rats (using a 50% sulfuric acid aerosol)
provides evidence of slight changes in the laryngeal epithelium at the
lowest concentration tested, 0.3 mg/m3 Other experimental studies in a
range of animal species suggest respiratory tract effects on repeated
exposure to concentrations around 0.3 mg/m3, with the possibility of
effects of some health significance even at concentrations down to about
0.1 mg/m3.
Taking into account the overall database, and with the concern for
potential human carcinogenicity in mind, SCOEL concluded that long-
term exposure should be maintained below 0.1 mg/m3 in order to provide
sufficient reassurance of avoidance of possible adverse consequences for
the respiratory tract epithelium. Hence SCOEL recommends an 8h TWA
limit of 0.05 mg/m3 in order to satisfy this requirement. SCOEL
appreciates that the reliable measurement of exposures at and around the
limit value proposed is challenging. In some circumstances there might
be interference from sulfate salts also present in the atmosphere.
However, from the most recent evidence presented to SCOEL and from
the assessment made in the Annex it appears that there are measurement
techniques available that are compatible with the proposed limit.
In terms of health protection, SCOEL considered that it would be
desirable to recommend a STEL of 0.1 mg/m3 to avoid short-term irritant
effects. However, at present there is no available measurement method
which can accommodate a short-term limit at this value (see Annex)
There is no evidence that H2SO4 can penetrate undamaged skin to cause
any signs of systemic toxicity, hence there is no requirement for a ‘Sk’
notation.
68
References
Company.1984.
69
70