Caustic Recovery

Preliminary tests for design of a Caustic Recovery Pilot Plant for Kamal
Ltd.
Pakistan

Test Report

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Caustic Recovery Tests

Contents
Introduction ............................................................................... 3
Process Description.................................................................................... 3
Target ......................................................................................................... 3
Problem Statement .................................................................................... 3

Tests ........................................................................................... 5
Colours present in washing effluent .......................................................... 5
Indigo (Vat Blue CI Reduced Vat Blue1).................................................................... 5
Properties ......................................................................................................................... 6

CI Sulphur Black 1 .................................................................................................. 6

Properties ......................................................................................................................... 6

Chemical analysis ....................................................................................... 7

Challenge.................................................................................... 7
Procedure ................................................................................................... 8
Filtration ................................................................................................................ 8

Discussion and Conclusion ....................................................... 12

Alternative 1............................................................................................. 12
Alternative 2............................................................................................. 13

Outlook ..................................................................................... 14

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Caustic Recovery Tests

Introduction
In textile processing plants, Denim fabric is treated with caustic soda in a
mercerization process and then washed to remove un-treated caustic soda.
Process Description
The industrial client is a denim manufacturing unit in Karachi, Pakistan. The client
process description is that fresh caustic soda, used in the mercerization process, is in
the concentration of 25-30 B. After the mercerization, the fabric is washed to
remove the residual caustic at a flow of 120 litre/min and a temperature of 65C.
The washing effluent contains 4-5 B caustic soda with contamination of:
1. Indigo colour,
2. Sulphur colours (Black, Yellow Brown) and
3. Sizing material (Maize starch, PVA, Acrylic and wax).
Target
The target is to recover & reuse Caustic Soda from the spent washes. Normally, no
denim manufacturer in Pakistan recovers caustic soda due to the contaminations
mentioned in the section above. However there is great saving potential that exists in
this option. The industrial company is interested to get a solution for this problem,
and wants to become Pilot Project under SCI-PAK.
The target is to recover caustic from 7200 litre per hour 4-5 B effluent. The quality
requirement for process is that the recovered caustic solution must be colourless,
as the fresh solution of caustic used for mercerization must always be colourless.
Problem Statement
To recover Caustic Soda from denim fabric mercerization waste liquor. The spent
liquor contains 4-5 B (see Figure 1) caustic soda at a flow rate of 7,200 liters per
hour.

Figure 1: concentration of caustic soda in g/kg and B

The caustic soda could be recovered and reused by caustic recovery plant, but it
cannot due to the contamination problems mentioned above.

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Caustic Recovery Tests

In the above context, the sample was collected from the client. The sample was
bluish-dark in colour (see Figure 2). The sample was filtered and the resultant colour
is yellowish (Figure 3), which makes it unusable.
No chemical analysis had been performed on the solution yet.
In this aspect, technical assistance was required for modifications in the design of
the Caustic Recovery process, for further purification of the liquor, in order to get a
colourless solution.
PH-value of the washing effluent

Ph of Effluent is 13.2 and Be 4-6

Trade name of the colors

CI sulpher Black 1(HS Code# 3204-1910)

Vat Blue CI Reduced Vat Blue1(HS
Code#3204-1510)

Table 1: pH-Value and trade names of colours in the washing effluent

Test filtrations with the washing effluent had been done, with the result of a cleaned,
but not colourless solution (see figure 2). The Filtration membrane used in this
process is unknown.

Figure 2: Sample of washing

effluent

Figure 3:Sample of washing effluent

after filtration

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Caustic Recovery Tests

Figure 4: Washing effluent (left) and filtered effluent (right) as obtained from Kamal

Tests
In order to determine the right membrane for separating the colors present in the
washing effluent, first the chemical build-up of these colors had to be known.
Colours present in washing effluent

Indigo (Vat Blue CI Reduced Vat Blue1)

Indigo dye is an organic compound with a distinctive blue color. Historically, indigo
was extracted from plants, which was of economical importance because blue dyes
were once rare. Nearly all indigo produced today several thousand tons each year
is synthetic.

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Caustic Recovery Tests

Properties
Indigo is a dark blue crystalline powder that sublimes at 390392 C. It is insoluble
in water, alcohol, or ether but soluble in DMSO, chloroform, nitrobenzene, and
concentrated sulfuric acid.
Chemical Build-up

Chemical Formula:

C16H10N2O2

Molar Mass:

262.27 g/mol

Appearance:

dark blue crystalline powder

Density:

1.199 g/cm3

Melting point:

390392 C

Solubility in water:

insoluble at 20 C

Table 2: Properties of Indigo

CI Sulphur Black 1

Properties
Sulphur black is an important class of dye for the coloration of cellulosic, being in
existence for nearly a hundred years.
The good fastness properties, cost effectiveness & ease of applicability under
different processing conditions (semi-continuous and continuous) make it one of the
most popular dyestuffs.
Chemical Build-up

Chemical Formula:

C6H4N2O5

Molar Mass:

184.11 g/mol

Density:

1.87 g/cm3

Boiling point:

660C at 760 mmHg

Table 3: Properties of C.I.Sulphur Black

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Chemical analysis
The samples, collected from Kamal were first subjected to a number of tests:
pH-value
Redox potential
electrical conductivity
The results can be found in the following table:
Parameter

Unit

Raw
Caustic
pH
12.88
Temperature C
23
Redox
mV
-338
Electrical
mS/cm 360
Conductivity

Filtered
Caustic
12.68
23.1
-333
327

400 500
Da Filtrate
13.08
21.2
-357
407

200
Da
Filtrate
13.14
21.22
-357
339

Table 4: results from chemical analysis of the samples collected from Kamal

Challenge
The idea was to use a two step membrane process to remove the colors from the
washing effluent. For this purpose, membranes had to be found, which are resistant
to high pH-values, since the pH of the washing effluent is between 13.2 and 13.5.
Two membranes where finally identified as pH-resistant:
Membrane
pH-range
molecular weight cut-off (MWCO)
[Dalton]
Maximum operating pressure [bar]
Processing Temperature [C]
Producer

1
1-14
400-500

2
0-14
200

40
5-95
Microdyn
Nadir

35
0-70
Koch
Membranes

Table 5: pH-resistant Membrane types identified

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Procedure
The samples collected from Kamal were filtered, using membranes obtained from the
producers mentioned in Table 5. The apparatus used was a small-scale test
membrane system.

Figure 5: Small-scale test membrane system used for the experiments

Filtration
400-500 Dalton cut-off size Membrane (Microdyn Nadir)
Testing Conditions:
Operating pressure
Membrane dfferential pressure
U
Volume flow of caustic soda over membrane
Membran Area
Test Temperatur
Flow velocity over Membrane
Kinematic viscosity of water (22C)
hydraulic Pipe diameter
Reynolds Number

35
3
1000
1,0E-05
1,710E-03
22
0,67
9,5650E-07
0,00375
2614

bar
bar
1/min
m/s
m
C
m/s
m/s
m
transition

Table 6: Testing Conditions of the first filtration step (MWCO 400-500 Da)
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Figure 6: Permeate of the 400-500 Da filtration (left) and the filter sample obtained
from Kamal (right)
The permeate of the 400-500 Dalton Nano-filtration showed a lighter colouring than
the sample collected from Kamal (see Figure 6).
The permeate was further used in the next filtration step, using the 200 Dalton
Nano-filtration membrane from Koch Membranes.

Testing Conditions:
Operating pressure
Membrane dfferential pressure
U
Volume flow of caustic soda over membrane
Membran Area
Test Temperatur
Flow velocity over Membrane
Kinematic viscosity of water (22C)
hydraulic Pipe diameter
Reynolds Number

35
3
1000
1,0E-05
1,710E-03
22
0,67
9,5650E-07
0,00375
2614

bar
bar
1/min
m/s
m
C
m/s
m/s
m
transition

Table 7: Testing Conditions of the first filtration step (MWCO 200 Da)

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Figure 7: Permeates from the filtration tests

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Original (as obtained from

Kamal)
Filtrate
Clean NaOH (3%)

Caustic Recovery Tests

Colouration [m-1]
430nm 545nm 610nm
Raw
9,61
3,18
1,94
Filtrate
8,39
2,09
1,29
400 500 Da 4,02
0,906
0,490
200 Da
2,68
0,608
0,403
0
0
0

Figure 8: Colouration of the different solutions, indicated by spectral absorption

coefficient

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Caustic Recovery Tests

Discussion and Conclusion

The caustic soda present in the spent wash from the mercerisation process at Kamal
could be recovered, using a two-step nano-filtration process. The recovered Caustic
soda solution would thereby become greatly de-coloured (see Figure 8), however even with a reverse osmosis filtration - a completely colourless liquid is not possible
to obtain, due to the diffusion of dye molecules through the membrane (in the long
term).
It is therefore to be decided, to what degree the recovered caustic soda
has to be decoloured, in order to be re-usable in the mercerisation process.
Alternative 1
An alternative solution might be to use a diffusion dialysis process and/or electrodialysis process to recover the caustic soda from the spent wash. Such processes are
actively being used in recovery processes for acids and bases in small and large scale
applications.
In diffusion dialysis, the potential of a concentration difference is instrumental for
mass transfer. Pore-free ion exchange membranes are used in this case. Hence, free
strong acids (acid dialysis) can be recovered by using anion exchange membranes
and free strong bases (base dialysis) by using cation exchange membranes.

Figure 9: Diffusion Dialysis, explained by means of Anion exchange process

The dialysis process is applied for the recovery of free acids or bases from spent
treatment bath solutions in surface finishing and textile processes. The spent bath
solution is separated in a chamber in counter-current flow and via an ion exchange
membrane and is then routed to a second chamber through which water flows. The
free acid or base is able to permeate while the salts are retained. Depending on the
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Caustic Recovery Tests

process design, up to 95% of the free acid and up to 80% of the base can be
recovered in this way and returned to the production process.

New membranes, which have high chemical and thermal resistance, have been
developed for use in acid dialysis, thus allowing troublesome process solutions to be
treated also. When applied at industrial level, these membranes can be easily
cleaned because of their improved resistance to oxidation as well as their high
chlorine tolerance.
New membrane modules combined with highly permeable membranes have been
developed to reduce investment costs.
Alternative 2
The third option would be a combination of a micro- and/or nano-filtration process
and a diffusion dialysis/electro-dialysis process.
Hybrid processes combining diffusion-/electro- dialysis and/or micro-/nano-filtration
have been developed for operations with a low salt concentration and high volume
flows, hence reducing investment costs effectively. Typical applications for this hybrid
process can be found in acid as well as base recovery.

Figure 10: Possible Set-up of the pilot plant for Kamal Ltd.

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Caustic Recovery Tests

Outlook
In order to find the optimum solution for recovering the caustic soda at Kamal Ltd.,
additional tests are necessary.
These tests could be done by TTZ, which would require additional samples of about
200-300 l of spent wash.
Alternatively, service providers/producers of the envisioned processes/equipment
could be contacted, in order to undertake tests and install the pilot plant at Kamal
Limited. Either way, these service providers/producers would have to be contacted at
one point, to install the pilot plant at Kamal Limited.
Following is a table of the most promising service providers/producers, who are able
to undertake further pilot tests and install the pilot plant:

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Service
Provider/
Producer
Microdyn Nadir
GmbH

Koch Membrane
Systems

OSMO Membrane
Systems GmbH

Process, Equipment

pH-resistant (1-14) nanofiltration membranes with a

MWCO of 400-500 Da

pH-resistant (0-14) nanofiltration membranes with

MWCO of 1000 Da and 200
Da
Pilot plants
Complete Systems

Reverse osmosis
Nanofiltration
Ultrafiltration
Microfiltration
Electro dialysis
Diffusion dialysis

Services

Product information for membranes and

modules
Technical advice and recommendations for
application
System and processing advice
Process and method evaluation
Assistance in monitoring, analyzing, and
solving system issues
Rapid availability of superior custom
formulated KMS Membrane Cleaners and
Antiscalants
Expert fitting of Replacement Parts and
Membranes
State-of-the-art Remote Monitoring and
Data Acquisition
On-site implementation by highly qualified
KMS Field Service Engineers
Comprehensive hands-on Training
Emergency Response and Assistance
Pilot System for pre-purchase performance
evaluation and after-the-sale diagnostics
Proof of concept
Laboratory examination and pilot
projecting
Basic and detail engineering (CAD in 2D
and 3D)
Implementation and automation

Contact

www.microdyn-nadir.de
info@microdyn-nadir.de
+49 (0) 611 - 962 6001
www.kochmembrane.com
farrel2m@kochind.com
hatchl@kochind.com

www.osmo-membrane.de
info@osmo-membrane.de
General manager: Dipl.Ing. Christian Steine

Titel (nderung mit Doppelklick)

DEUKUM GmbH

Pilot plants for rent

Documentation
Start-up
After sales service and spare parts supply

+49 (0) 7150 / 2066-0

Elektrodialysis
Membranelektrolysis
Diffusiondialysis
Pilot plants

Production, supply and set-up of

Membrane stacks for electrodialysis and
diffusion dialysis
Laboratory- and Pilot- testing
Engineering, plant design and consulting

www.deukum.de
info@deukum.de
HANS-JRGEN RAPP
Dr. Ing.
Verfahrenstechnik
Geschftsfhrer
+49 (0)70 22 / 47 06 95

FuMA-Tech
GmbH

Electrodialysis
Bipolar membrane
technology
Membrane electrolysis
Diffusion dialysis
Reverse osmosis
Nanofiltration
Ultrafiltration
Microfiltration

Authorised analytical laboratory

Applied engineering workshop
Mobile pilot plants
Feasibility studies

www.fumatech.com
office@fumatech.de
Yervant Bohdjalian
(Membrane Technology)
T: +49 6894 9265-23
Dr. Karl Danz
(Components & Plant
Engineering)
T: +49 7042 97024-23

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WAG-Freiburg
GmbH

Caustic recovery from

mercerizers and other
sources
Wedge filtration of
effluents, strong and weak
lyes with wear-resistant
filters
Color Removal from waste
water and process water.

Piping diagrams
Process development
Controll-system design
Software-services
Ingeneering services
Pilot-plants
Experimental projects

Table 8: Service providers/producers for pilot plant tests, design and set-up

www.wag-freiburg.de
info@wag-freiburg.de
+49 (0)7668 / 95 20 74
(sales)
+49 (0)7668 / 95 20 75
(service)