Confidential

Octava Mesa Redonda de Plantas

de Acido Sulfrico
Sulfuric Acid Urban Myths and Legends
Confidential
A fictional tale that circulates widely, is told and retold
with differing details, and is supposedly true.

An urban myth, also known as an urban
legend, is
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Sources of Myth and Legend in an Industrial Setting
With limited process information, conjecture can
become reality

Actual events are embellished (a good story spreads
fast!)

Opinion from a credible source becomes reality

Word of a bad experience filters through the industry
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Myth 1:
Which is Better?
>
?
8% V
2
O
5
7% V
2
O
5
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A Little About The Makeup Of Catalyst
Catalysts are comprised of > 80% silica support . . .
that comes from diatomaceous earths.
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Which Provides Great Surface Area For The Catalyst And Gas
To Interact
Silica
Support
Catalyst Extrudates: Pores Contain Active Phase
That Becomes Molten at
Reaction Temperatures
Fractional Liquid Loading
Typically, 30 to 40% pore
volumes are filled.
Schematic of catalyst pores
Active phase
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The Myth Busting Machine
Adiabatic Integral Reactor
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The Myth Busting Machine
Multiple
Thermocouples
Gas sampling
along the length
of the catalyst
bed
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Test Results
Catalysts A and B are identical in composition and
made at same time in our catalyst plant.
Which Catalyst is More Active?
Catalyst A Catalyst B
Particle size (mm) 0.074 11.6 0.074 11.6
Total pore Volume (cm
3
/g) 0.682 0.609
K/V ratio 2.9 2.9
V
2
O
5
(wt%) 7.2 7.8
Fractional Liquid Loading 0.36 0.46

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The Data
62.6%
11.5% SO
2
, 9.5% O
2
,
420
o
C Inlet Temperature,
100 SLFM
Adiabatic Integral Reactor Results
More active A
contains less
vanadium
Confidential
Theoretically Speaking
0
25
50
75
100
125
150
175
200
0.00 0.15 0.30 0.45 0.60 0.75
W
V
/ F
SO2
, g V-s/mol
-r
SO2
,
mol/g V-s
475
o
C
MECS-A
7.2 % V
2
O
5
MECS-B
7.8% V
2
O
5
Reaction Rates Compared Using Differential Reactor Data
Catalyst A with less V shows
nearly twice reaction rate
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What Really Matters in Catalyst Design

Catalyst activity arises from:

* Process conditions
* Catalyst composition
* Catalyst porosity
* Internal mass and heat transfer
- diffusion, reaction & effectiveness factor
2D Catalyst Cross Section
3D Catalyst Cross Section
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The Most Active Catalyst Will Not Necessarily
Contain Most Vanadium

Many Factors Play Into Making The Most
Effective Use of the Vanadium
Higher Vanadium Content Improves
Sulfuric Acid Catalysts Activity
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Myth 2: When it comes to mist, what
happens in the tower, stays in the
tower

Mist Formation
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Competing SO
3
Mechanisms in an
Absorber
Desired mechanism

Absorption of SO
3
gas into the circulating acid


Reaction of absorbed SO
3
gas with H
2
O in the liquid


Competing reaction

SO3 (g) + H2O (g) -> H2SO4 (mist)

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The Mist Busting Machine
VISIBLE
TOWER
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Opacity Caused by Vapor Phase Reaction of H
2
O & SO
3

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Vapor Pressure of H2O and SO
3
Over H
2
SO
4

0.0000
0.1000
0.2000
0.3000
0.4000
0.5000
0.6000
0.7000
0.8000
99.9 99.5 99.0 98.5 98.0 97.5 97.0 96.5 96.0 95.5 95.0
% H2S)4
V
a
p
o
r

P
r
e
s
s
u
r
e

(
m
m
H
g
)
SO3 tower top
SO3 tower bot
H2O tower bot
H2O tower top
104 C
82 C
104 C
82 C
Mist Forms
H
2
O
vapor
SO
3
Final Absorber Conditions
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Vortexing Can Cause Problems as Well
Gas Inlet Duct CFD Model
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Diffusion of H
2
O vapor and vortexing are significant and
can cause mist to migrate outside of the tower
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Myth No. 3:

A stick test is only qualitative and
doesnt tell me much about what the
problem is.
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How do you relate spot size to the type of problem?
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Calibrate a Stick Test!
Air brush supplied fine
mist particles to stick
And the mist was
measured by a Welas
laser particle counter
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Measured Particle Size Distribution
0
2
4
6
8
10
12
14
16
0
.
2
3
7
0
.
2
5
5
0
.
2
7
4
0
.
2
9
4
0
.
3
1
6
0
.
3
4
0
.
3
6
5
0
.
3
9
2
0
.
4
2
2
0
.
4
5
3
0
.
4
8
7
0
.
5
2
3
0
.
5
6
2
0
.
6
0
4
0
.
6
4
9
0
.
6
9
8
0
.
7
5
0
.
8
0
6
0
.
8
6
6
0
.
9
3
1 1
1
.
0
7
5
1
.
1
5
5
1
.
2
4
1
1
.
3
3
4
1
.
4
3
3
1
.
5
4
1
.
6
5
5
1
.
7
7
8
1
.
9
1
1
2
.
0
5
4
2
.
2
0
7
2
.
3
7
1
2
.
5
4
8
2
.
7
3
8
2
.
9
4
3
3
.
1
6
2
3
.
3
9
8
3
.
6
5
2
3
.
9
2
4
4
.
2
1
7
4
.
5
3
2
4
.
8
7
5
.
2
3
3
5
.
6
2
3
6
.
0
4
3
6
.
4
9
4
6
.
9
7
8
7
.
4
9
9
8
.
0
5
8
8
.
6
6
9
.
3
0
6
0
20
40
60
80
100
120
140
160
180
Number of Particles
Cumulative Number of Particles
Mean = 0.4 m
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View of stick after spraying
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Comparing Acid Spray to Paint Spray Sticks
Acid
Paint
Paint
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Microscopic view of a paint large spot
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View of smaller spots
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Conversion of Droplet to Spot
Volume of mist droplet
4/3R
3
1 m = 0.52 m
3
3m = 14 m
3
5 m = 65 m
3
25 m = 8,180 m
3
Diameter if a spot is 0.1m thick
R
2
L
1m = 2.5 m
3m = 15 m
5m = 30 m
25m = 325 m
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Microscopic View of Spots on the Stick
Paint
Acid
Average = 15 m Average = 15 m
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Smallest particle found
They do not impinge on the stick!!
Although a majority of the particles
are sub-micron
1m droplet = 2.5 m spot
Stick test >1m
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A stick test is only qualitative
With the proper calibration, the venerable stick test
takes on new meaning!

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Pop Quiz!
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Condensation or Mechanical Mist?
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Mechanical Re-entrainment problem
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Is there a problem here?
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What if the stack looked like this?
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And the Gas Above the Mist Eliminators
looked like this?
SO
3
gas above tubesheet
Mist above tubesheet
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Clean 3 minute stick test
Sub-micron mist or trace SO
3

Slight opacity in stack
Sub-micron mist or trace SO
3


Clear gas above candles
SO
3

Cause: SO3 slip due to an absorption problem
Summarizing the Data
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Myth No. 4:

Can a sulfuric acid spill
cause a fire?
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Trial 1: H
2
SO
4
+ C
12
H
22
O
11
(sugar)
H
2
SO
4
+ C
12
H
22
O
11
12C + 11H
2
O
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Trial 2: H
2
SO
4
+ C
12
H
22
O
11
+ KNO
3
(rocket candy)

H
2
SO
4
+ C
12
H
22
O
11
+ KNO
3

12C + 11H
2
O + KSO
4
+ H
2
O + NO2
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Trial 3: H
2
SO
4
+ C
12
H
22
O
11
+ Secret Sauce

6H
2
SO
4
+ C
12
H
22
O
11
+ 12KClO
3

12CO
2
+ 17H
2
O + 6KCl
2
+ 6KSO
4
+SO
2

Confidential
Can a sulfuric acid spill cause a fire?
Yes, but you really have to try!
Confidential
MECS and Lewis Pumps Hopes
You Enjoyed our Version of
MYTH BUSTERS