Electrolyte Process Design

for HCl Separations

with PRO/II and OLI
OLI Simulation Conference 2016
25-26 October 2016
Dr.-Ing. P. Pöllmann, AQSim EUROPE
OLI Systems, Inc.

Cited from:
http://www.olisystems.com/about-us
OLI Systems, Inc.

Cited from:
http://www.olisystems.com/technology-scope
OLI and SimSci partnership: two levels
• OLI embedded in PRO/II as PRO/IIe
• SimSci purchased the OLI model in 1983
• OLI full support provided for the next 33 years
• All OLI solver improvements made for the PRO/IIe software
as well as for OLI
• All OLI database improvements were made for only the PRO/IIe
components
• PRO/IIe contains a subset of the components in OLI’s AQ (Aqueous)
model
• OLI MSE Engine in PRO/II as a joint product with OLI - SimSci
• An additional capability beyond PRO/IIe
• Full OLI’s AQ model databank
• Using the OLI MSE (Mixed Solvent Electrolyte) framework
• Makes accurate simulation of highly concentrated
systems possible

OLI MSE Engine in PRO/II

Process Simulation … Flowsheet Given
Classical Approach Using a Process Simulator:
1) Draw flowsheet
2) Define components
3) Select thermodynamic methods
4) Supply data for feeds
5) Supply operating conditions for unit operations
6) Run
7) Analyse results
8) New operating condition? If yes, then 5)
9) New feed case? If yes, then 4)
10) Communicate results
Process Design … Flowsheet Unknown
Classical Approach:
1) Define process design objective (PDO)
2) Define components
3) Select thermodynamic methods (and check validity)
4) Supply data for feeds (representative to PDO)
5) Draw or modify flowsheet
6) Supply operating conditions for unit operations
7) Run
8) Analyse results
9) PDO fulfilled? If no, then go to 5)
10) Communicate new flowsheet (decide alternatives)
11) Simulate feed cases and operating points
Process Design Objective

Extractive HCl
HCl + Water
Distillation Water
Hydrochloric
Acid
Process Design Objective
This presentation

Extractive
HCl + Water Distillation
Extractive
Hydrochloric HCl
Desorber
Acid Water

BRINE
Regenerator
BRINE
Process Design Objective … Extractive Desorber

HCl + Water HCl

Extractive
BRINE Desorber BRINE + Water
Extractive agent
in BRINE:
CaCl2 in aqueous
solution.
Thermodynamic Model Validity
VLE of Hydrochloric Acid with Calcium Chloride
1 atm / Parameter: CaCl2 wt.-% / lines: OLI MSE / dots: Lutz (1994)
100

90

80
0

70 10
20
HCl in vapor, wt.-%

60 30
40
50
50

40 0 exp
10 exp
30 20 exp
30 exp
20
40 exp
50 exp
10

0
0 5 10 15 20 25
HCl in liquid, wt.-%
Thermodynamic Model Validity

Dots:
Experimental
data

Line:
OLI MSE model
prediction

Validation Plot is property of OLI Systems, Inc.

Thermodynamic Model Validity
Back in 2003, The DOW Chemical Company
distributed a handbook on calcium chloride
products. They show this diagram for the
temperature increase in dissolving a special
product or anhydrous CaCl2 in water.

For example, the heat generated in preparing a

40% calcium chloride solution with anhydrous
would result in a temperature increase of
approximately 91 K (164 F).

The OLI MSE model predicts 91.8 K.

Cited from:
http://www.osi-univers.org/IMG/pdf/CalciumChloridHandbook-2.pdf
Feed Data
ACID Feed:
25°C
4555.6 Water
1 t/h HCl,
1000HCl as 18% acid, 25°C
0CaCl2

HCl + Water HCl

Extractive
BRINE Desorber BRINE + Water
BRINE Extractive Agent:
boiling
10000Water 10 t/h CaCl2,
0HCl as 50% aqueous,
10000CaCl2
boiling
Chemistry Setup OLI Chemistry Wizard
1) Launch OLI Chemistry Wizard 2) Select MSE Framework

3) Select Components 4) Finish to find dbs file

Chemistry Setup PRO/II
1) Thermo Button 2) Modify Button

4) Specify in Terms of Apparent

Species

3) Find
Component
Selection list
extended 
Process Design Objective … Rules of the Game
Keep specifications fixed.
Free to modify everything else.
ACID Feed:
25°C
4555.6 Water 1 t/h HCl,
1000HCl as 18% acid, 25°C Product:
0CaCl2 HCl gas dry 0°C
HCl + Water HCl
Extractive
BRINE Desorber BRINE + Water
By-Product:
BRINE Extractive Agent: Dilute BRINE,
boiling
10000Water
10 t/h CaCl2, reasonable HCl
0HCl as 50% aqueous, Supply 1 MW impurity
10000CaCl2
boiling heating duty
 This will be in the
Evaporator focus next. 1000 HCl
should be Unit E1 is supposed to
V-E1 kg/h - mix ACID with BRINE,
ACID vapor
25°C
- heat the mixture up,
910.6 Water
4555.6 Water 696.9 HCl Result - evaporate it partially,
1000HCl 0 CaCl2 - and separate V from L, by a
0CaCl2 VLE calculation.
L-E1
liquid
Insight 1) HCl is squeezed out nicely
13645 Water 2) … but also loads of water,
303.1 HCl
so that product dryness
10000 CaCl2
E1: Flash specification is violated.
Duty = 1 MW 3) There is an intolerable loss
What next …
BRINE Pressure Drop = 0 of HCl via the liquid.
boiling
10000Water
Pressure is 1 atm
0HCl
10000CaCl2
 Dry the product gas
by default Specification
by condensation ...
Condenser 0°C
Since HCl is known to be
a gas, unit E2 is supposed
This is the new thing. to cool vapor V-E1 down
ACID
25°C to 0°C to condense out
4555.6 Water most of the water.
1000HCl
0CaCl2
V-E2 is missing. E2 has
achieved total condensation.
E2: Flash
Actually, V-E1 is gaseous
Temperature = 0°C
hydrochloric acid with 43%
Pressure Drop = 0
E1: Flash HCl, which is fully condensed
This will be in the
Duty = 1 MW at 11°C.
focus next.
BRINE dP = 0
boiling
10000Water
These data are same as  Go for less aggressive
0HCl before. From now on,
10000CaCl2 only new information condensation ...
shall be shown.
Condenser 50°C
V-E2
Unit E2 is re-specified to
vapor, 50°C
1.99 Water
cool V-E1 down to 50°C.
160.6 HCl
0 CaCl2

V-E2 is present now. It is

L-E2 HCl gas, saturated with
liquid, 50°C
water at 50°C.
908.7 Water
536.2 HCl
0 CaCl2 By balance, the loss of HCl
L-E1
via liquids L-E1 and L-E2 is
liquid
13645 Water
an intolerable 840.
303.1 HCl E2: Flash
10000 CaCl2 Temperature = 50°C
Pressure Drop = 0
 Find a place for L-E2
in the process ...
Reflux
V-E2 Condensate L-E2 is
vapor, 50°C
connected back to the
5.447 Water
439.7 HCl
evaporator E1 as a
0 CaCl2 process reflux.

By the principle of
fractionation, partially
refluxing separated
material, the loss of HCl
L-E1 is brought down to 560
liquid now.
14550 Water
560.3 HCl
10000 CaCl2

 Go for final product

specification …
Condensation Train
Vapor V-E2 at 50°C is dry
E2: Flash E3: Flash enough to be cooled
T = 50°C T = 0°C V-E3 further down, to 0°C.
dP = 0 dP = 0 HCl gas, 0°C
0.0696 Water Condensates are
437.5 HCl base collected and fed back as
0 CaCl2
a mix to the process.

V-E3 is HCl gas, saturated

with water at 0°C,
M1: Mixer meeting product
dP = 0 specification on the gas
side. But still, the loss of
HCl is prohibitive.
L-E1
liquid  Split the combined
14555 Water
562.5 HCl
jobs done at E1 …
10000 CaCl2
Reboiler
V-E3
HCl gas, 0°C
0.104 Water
652.0 HCl + 214.5 The job to introduce
0 CaCl2 heating duty to the
system is taken out as an
extra step.

The split of jobs was very

beneficial, because it
corresponds to the
addition of one
separation effect to the
fractionation.

T1: Flash L-E1

Duty = 0 liquid
dP = 0 14555 Water
348.0 HCl  Split the combined
E1: Flash 10000 CaCl2 jobs done at T1 …
Duty = 1 MW
dP = 0
 V-E3
HCl gas, 0°C
0.105 Water
Feed Mixer 657.0 HCl
0 CaCl2
+ 5.1
The job to mix the feed
V-T1 media is taken out as an
vapor extra step, done in unit
50.2 Water T1.
106.9 HCl
0 CaCl2 With the benefit in HCl
production being only
S1: Flash small, it is highly
Duty = 0 recommended to mix the
dP = 0 very different media ACID
and BRINE in front of the
L-E1 system. The more so, as a
liquid
vapor is released by the
14555 Water
343.0 HCl
heat of mixing.
10000 CaCl2
 Test the other place
T1: Flash
Duty = 0
for the reflux …
dP = 0
 V-E3

Reflux plus Feed Mixer HCl gas, 0°C

0.106 Water
665.3 HCl + 8.3
0 CaCl2

V-T1 Condensate reflux is

vapor
connected down to the
62.7 Water
+ 62.8 169.7 HCl feed mixer tank, from
0 CaCl2 where material is
transferred to the
separation anyway.

Very strong hydrochloric

L-E1 acid condensate increases
liquid pre-evaporation in T1,
14555 Water which is welcome.
334.7 HCl
10000 CaCl2

 Try stronger BRINE …

 V-E3

Stronger Brine HCl gas, 0°C

0.137 Water
860.2 HCl + 194.9
0 CaCl2

Water, the solvent, or

carrier of extractive
species, is reduced.

… tremendous increase
of production. The
10 t/h CaCl2 as system needs to process
55% aqueous less water. By the logic of
the example, fixed
BRINE L-E1
boiling liquid
reboiler duty can be
8181.8 Water 12737 Water turned into more
0 HCl 139.8 HCl separation effect.
10000 CaCl2 10000 CaCl2

 Look into heat recovery …

 Heat Recovery / 1 of 2
V-E3 Idea: Preheat feed ACID
E5 E4
required available
HCl gas, 0°C to 90°C, by use of latent
0.144 Water heat of condensation.
Cold T Duty Hot T Duty E4: Simple HX + 44.1
°C 1e6 kJ/h °C 1e6 kJ/h 904.3 HCl
90 1.216 100 0.826
Hot T = 100°C 0 CaCl2 As it appears, the target
95 1.689 dP = 0 of 90°C should be
feasible.
E5: Simple HX
Required and available
Cold T = 90°C
energy flows need to be
dP = 0
matched, and a feasible
temperature difference
for the heat transfer
L-E1 must be respected.
liquid
12737 Water
95.7 HCl
10000 CaCl2  Rearrange the
flowsheet …
Heat Recovery / 2 of 2
New:
HCL - Feed
gas, 0°C interchanger hot
0.145 Water and cold sides
+ 8.0 912.3 HCl combined
0 CaCl2
- Condensers
followed by
tanks
- Utilities to
E2: Simple HX condensers
Cold T = 90°C - Major flowsheet
dP = 0 L-E1 rearrangement.
liquid
12737 Water
87.7 HCl
10000 CaCl2

 Invest one
more stage …
Separation Stage #2 HCL
gas, 0°C
0.153 Water
+ 50.0 962.3 HCl Flash stack
0CaCl2 model of
fractionated
distillation with
2 stages.
S1, S2: Flash
Duty = 0 Having checked
dP = 0 everything else
is the right time
to invest for
another stage.
L-E1
liquid
12737 Water
37.7 HCl
10000 CaCl2

 Go for a column …
 HCL

Column gas, 0°C

0.158 Water
992.2 HCl + 29.9 Wasting 1% of
0 CaCl2
feed HCl is taken
1 t/h HCl as reasonable in
as 18% acid T5: Distillation the example.
5 stages
ACID L-T1 to stage 1 The previous
25°C
No condenser sequence of steps
4555.6 Water
1000HCl
Kettle reboiler prove the shown
0CaCl2 Duty = 1 MW system to be
dP = 200 mbar feasible in theory
to separate 18%
HCl acid, using a
BRINE L-E1 specific energy
boiling liquid demand of 1 MW
8181.8 Water 12737 Water
0 HCl
per t/h, exclusive
7.8 HCl
10000 CaCl2 10000 CaCl2
the regeneration
of extractive
10 t/h CaCl2 as agent.
55% aqueous
Process Design Step Impacts Base: 437.5
Column

Separation Stage #2

Heat Recovery (2 of 2)

Heat Recovery (1 of 2)

Stronger BRINE

Reflux plus Feed Mixer

Feed Mixer

Reboiler

0 50 100 150 200 250

Production Increase, kg/h

Extractive Distillation PFD following EN ISO 10628
Water HCl

ACID E2

E3
CW
C1
E4
CCW
T5
E5
Steam

E1
P3 T1 P1 P2 Steam

BRINE
Conclusions
An intuitive method for the design of the flowsheet connectivity for hydrochloric
acid separation by extractive distillation has been presented. The method is not
limited by the kind of extractive agent.

The process system makes use of pre-evaporation, which occurs at the point of
mixing feed acid with extractive agent, and which can even be enhanced by pre-
heating the feed acid by latent heat of condensation. This way, an energy saving
flowsheet can be suggested.

Thermodynamic properties, with heat effects in particular, can very rigorously be

predicted for the physico-chemical system Water / HCl / Calcium Chloride by the
MSE model of OLI Systems, Inc.

Thanks to smooth interfacing between the OLI Engine and PRO/II, process design
for electrolyte flowsheets can be performed very efficiently.
Contact:
 Feed Data … Takeout
Remark on feed:
At the end of the work we will be able to tell
Feed is 1 t/h HCl ACID
what effort is required to make approx. 1 t/h of
as 18% acid 25°C
4555.6 Water HCl gas, if this flow is given at a concentration,
1000HCl where ordinary distillation must fail.
0CaCl2

HCl + Water HCl

Extractive
BRINE Desorber BRINE + Water
Extractive agent BRINE
is 10 t/h CaCl2 boiling
Remark on extractive agent flow:
as 50% aqueous, 10000Water
0HCl VLE has suggested a good separation effect, if
coming from 40% of extractive species prevail. Shall this
10000CaCl2
regenerator hold for the BRINE + Water flow, then the
choice of 10 t/h CaCl2 makes sense, since
10 / (10 + 10 + 4.6) is approx. 0.4
 Feed and Utility Data … Takeout
Process System
Cooling Water pressure is 1 atm
Feed is 1 t/h HCl 32°C by default.
ACID
as 18% acid 25°C Saturated
4555.6 Water Chilling Medium Steam Utility and other pressures
1000HCl 25% CaCl2, -10°C not in the focus here.
0CaCl2

HCl + Water HCl

Extractive
BRINE Desorber BRINE + Water
Extractive agent BRINE
is 10 t/h CaCl2 boiling Steam Condensate
10000Water Chilling Medium
as 50% aqueous, -5°C
0HCl Cooling Water
coming from
10000CaCl2 40°C
regenerator
Evaporator … Takeout
Pressure is 1 atm 1000 HCl should Unit E1 is supposed to
by default be kg/h - mix ACID with BRINE,
ACID
25°C
- heat the mixture up,
4555.6 Water - evaporate it partially,
1000HCl
Specification - and separate V from L, by a
0CaCl2 VLE calculation.

E1: Flash Remark on heating duty:

Duty = 1 MW When 1 t/h HCl gas is dissolved in water to
BRINE Pressure Drop = 0 make hydrochloric acid with 18 % HCl, a heat
boiling flow of 536 kW is generated. The example
10000Water assumes a rough double should suffice to do
0HCl the reverse.
10000CaCl2