Problem Statement
Given ...
An aqueous feed mixture,
which contains 13 wt-% HCl and 0.5 wt-% HF
Question ...
Is it possible,
to produce an hydrochloric acid of 31 wt-% HCl,
with an HF impurity of 50 ppm maximum?
Solution ...
... see the following presentation
Ternary Mixtures
Ordinary Distillation, Splits and Products
Simple Distillation (Open Evaporation)
Simple vs. Ordinary Distillation
Ternary Mixtures
Ordinary Distillation, Splits and Products
Simple Distillation (Open Evaporation)
Simple vs. Ordinary Distillation
The Mathematics of Open Evaporation (OE)
Topological Structure of OE Diagrams
Singular Points (Pure Components and Azeotropes)
Examples of Possible OE Diagram Structures
xC
0.8
0.6
0.4
xCM
0.2
xBM0.4
0.2
0.6
B
0.8
xB
C (tC)
When, in the following, concentration
scales are not needed for discussion of
matter, the composition triangle will look
like shown here.
The diagram shall be isobaric. If necessary,
the constant pressure will be given
somewhere near or inside it.
The names of the pure components, if
necessary along with their boiling points in
parentheses, will be given at the corners.
The volatilities of the components shall be
A (most volatile) - B - C (least volatile).
p = constant
A (tA)
B (tB)
Ternary Mixtures
Ordinary Distillation, Splits and Products
Simple Distillation (Open Evaporation)
Simple vs. Ordinary Distillation
The Mathematics of Open Evaporation (OE)
Topological Structure of OE Diagrams
Singular Points (Pure Components and Azeotropes)
Examples of Possible OE Diagram Structures
D1, D2, D3
W2
F
W3 W1
W1, W 2, W 3
D1
A
D3
D2
D
The straight line through the point of
component C and the point of the feed F is
the locus of mixtures having the same ratio
of components A and B as the feed.
C
F
By nature of distillation,
from the feed location to the top of the
column, the ratio of more volatile A
increases to the expense of B,
W
W
D
A
D
C
W
W
F
D
A
D
C
W
F
D
A
Ternary Mixtures
Ordinary Distillation, Splits and Products
Simple Distillation (Open Evaporation)
Simple vs. Ordinary Distillation
The Mathematics of Open Evaporation (OE)
Topological Structure of OE Diagrams
Singular Points (Pure Components and Azeotropes)
Examples of Possible OE Diagram Structures
Residue curve
A liquid L shall be submit to open
evaporation in a heated pot. Above the
surface of the liquid L with composition x a
vapour V with composition y is formed in
thermodynamic equilibrium. The vapour
that is removed at the moment of
formation, carries volatile matter with itself.
V, y
L, x
.
Q
p = constant
L, x
V, y
A
V, y
L, x
.
Q
p = constant
L, x
L2
A
L1
V, y L
3
B
Ternary Mixtures
Ordinary Distillation, Splits and Products
Simple Distillation (Open Evaporation)
Simple vs. Ordinary Distillation
The Mathematics of Open Evaporation (OE)
Topological Structure of OE Diagrams
Singular Points (Pure Components and Azeotropes)
Examples of Possible OE Diagram Structures
D
A
D
There is evidence in literature, that the
boundary of the non-interesting ordinary
distillation products can be well
approximated by the residue curve running
through the point of the feed.
C
F
W
F
D
A
p = constant
?
?
?
Pure component
Binary azeotrope
Ternary azeotrope
binary
azeotropes
ternary
azeotropes
A (56)
A = Acetone
(55)
(65)
(65)
B = Benzene
C = Chloroform
(57)
EB = Ethyl Benzene
EG = Ethylene Glycol
C (61)
B (80)
C (61) (54)
M (65)
M = Methanol
O = Octane
O (126)
(117)
EG (135) (128)
EB (136)
xHF
1
HF (20C)
0.8
at 20 % HCl
0.6
Az. (113C)
0.4
0.2
p = 1.013 bar
0
0.2
H2O (100C)
0.4
0.6
Az. (109C)
0.8
HCl (-85C)
1
xHCl
xHF
1
HF (20C)
0.8
0.6
Az. (113C) ??
0.4
?
??
0.2
p = 1.013 bar
0
0
?0.2
H2O (100C)
0.4
0.6
Az. (109C)
0.8
HCl (-85C)
?1
xHCl
(< -85)
(< -85)
(...) = boiling
temperature (C) of
singular point (@ 1 atm)
(> 113)
(21...112)
Based on
the previously given theoretical
background
(> 113)
(21...112)
(> 113)
(21...101)
(< -85)
(101...108)
(101...108)
(101...108)
(< -85)
(< -85)
(> 113)
(> 113)
(21...112)
(> 113)
a saddle point
or a node
(101...108)
(101...108)
(101...108)
(21...101)
(< -85)
V, y
increasing
boiling
temperature
L1
V1
L, x
L2
V2
.
Q
p = constant
V, y
accumulated
vapour
In order to find out the nature of the HClwater azeotrope in the system of HCl, HF
and water, open evaporation experiments
have been performed in the chemical
laboratory at SGL Carbon, Meitingen.
Arrows indicate
increasing boiling
temperature
0.2
0.18
0.16
0.14
0.12
0.1
0.08
0.06
0.04
p = 1 bar
0.02
0
0.02
0.04
0.06
0.08
0.1
0.12
0.14
0.16
0.18
0.2
(< -85)
(< -85)
(...) = boiling
temperature (C) of
singular point (@ 1 atm)
(> 113)
(> 113)
(21...112)
(> 113)
(21...101)
(< -85)
(101...108)
(101...108)
(101...108)
0.35
measured
calc (Aspen)
0.3
0.2
Arrows indicate
increasing boiling
temperature
0.15
0.1
0.05
0
0
0.05
0.1
0.15
0.2
0.25
(A note on the difference between measured and OLI What has been calculated was a sequence of flashes,
taking every y as the new x, which is not a residue
curve, but topologically equivalent w.r.t starting and
ending points or dividing lines.)
HF (20C)
O (126)
Az. (113C)
(117)
p = 1.013 bar
HCl (-85C)
EG (135) (128)
EB (136)
xHF
HF (20C)
0.8
0.6
Az. (113C)
0.4
0.2
p = 1.013 bar
0
0.2
0.4
0.6
xHCl 0.8
HCl (-85C)
1.2
0.8
0.6
Distillation
boundary
But ...
0.4
0.2
D
0
0
0.2
0.4
0.6
0.8
1.2
0.8
0.6
Distillation
boundary
0.1 bar
0.4
1 bar
0.2
0
0
6 bar
0.2
0.4
0.6
0.8
1.2
1.2
F
W
0.8
0.6
0.4
0.2
0
0
0.2
0.4
0.6
0.8
1.2
0.4
F
0.2
Distillation
boundary
0.1 bar
1 bar
0.2
6 bar
Az. (165C 109C 57C)
0.4
Problem Statement
Given ...
An aqueous feed mixture,
which contains 13 wt-% HCl and 0.5 wt-% HF
Question ...
Is it possible,
to produce an hydrochloric acid of 31 wt-% HCl,
with an HF impurity of 50 ppm maximum?
Solution ...
The following process should work in principle!
1 bar
0.1
bar
HCl
6 bar
Water
HCl
HF
Water
HF (Az.)
Summary
For mixtures of HCl, HF and water ...
... Open evaporation experiments have been performed by
SGL Carbon, Meitingen, Germany
... The OLI MSE VLE model is supported by the
measurements
... The topological structure of open evaporation has been
postulated
... A distillation process for removing HF impurites from
hydrochloric acid has been suggested
... A preliminary design of the HF column was possible
using OLIs ESP simulator