Resources, Conservation and Recycling 37 (2003) 217 /226

www.elsevier.com/locate/resconrec

A systematic approach for water network

optimisation with membrane processes
Bernd Goers *, Markus Forstmeier, Barbara Wendler,
Günter Wozny
Technical University of Berlin, Institute of Process and Plant Technology, Sekr. KWT-9, Str. des 17,
Juni 135, D-10623 Berlin, Germany
Accepted 3 July 2002

Abstract

In this paper a systematic Concept for Retrofit Optimisation of Water Networks (CROWN)
is presented and applied to a liquid detergent production plant. For this problem the
identification of recycle loops, the choice of applicative unit-operations and the mathematical
optimisation of the system under economic constraints is considered. The importance of the
experimental verification of implemented devices is emphasised.
# 2003 Published by Elsevier Science B.V.

Keywords: Water network; Retrofit; Membrane separation; Detergents; Mathematical optimisation

1. Introduction

Economical impacts today force to look at water and wastewater networks of

industrial plants as an integrative part of the process. A systematic approach for the
retrofit optimisation of water networks therefore has to regard not only the relevant
treatment/regeneration unit operations. For the recycling of water and concentrate
(waste or resource) into the production process also the impacts of cross-
contamination, process sterility and the build-up of inert components have to be
considered.

* Corresponding author. Tel.:
/49-30-314-26695; fax:
/49-30-314-26915.

E-mail address: bernd.goers@tu-berlin.de (B. Goers).

0921-3449/02/$ - see front matter # 2003 Published by Elsevier Science B.V.

PII: S 0 9 2 1 - 3 4 4 9 ( 0 2 ) 0 0 1 0 1 - 5
218 B. Goers et al. / Resources, Conservation and Recycling 37 (2003) 217 /226

Up to now, the process integration of the water network generally appears to be a

retrofit problem, which becomes necessary due to process retrofit (capacity, product
quality), product changes or the disregard of the water system within the plant
design.
During the last decade systematic process synthesis and retrofit approaches for the
optimisation of water networks have been developed (Wang and Smith, 1994) and
improved throughout their application. A comprehensive overview is given by
Bagajewicz (2000). However, the regeneration of process streams is a design target,
which can only be achieved after the identification of the regeneration recycle loops.
This and the selection of a feasible process are a knowledge-based problem of the
synthesis process. An approach for the design of coupled treatment operations based
on a superstructure which is generated by a process and design rule data base is
presented by Lassahn and Gruhn (2000). For the solution based on the economic
objective a MINLP algorithm is used here.
In Fig. 1 the systematic used in this study is given and will also be used as the basic
structure of this article. Of course, for solving a retrofit problem there is no straight-

Fig. 1. Concept for retrofit optimisation of water networks CROWN. The experimental verification is
focused. The iterative loops after every design step are not displayed here.
 B. Goers et al. / Resources, Conservation and Recycling 37 (2003) 217 /226 219

forward recipe, but most of the iterative loops have not been visualised for reasons of
clearness.

2. Analysis of water system and problem description

As an industrial case study, the production of detergents in a multi-product batch

plant is regarded in this paper. The case study has been carried out at a liquid
detergent production site where 60 /80 different products are produced on 6
production lines as illustrated by Goers et al. (1998). About 100 000 m3 tap water
are consumed at this site. The plants are frequently cleansed by a cleaning in place
(CIP) system. The water/wastewater network of the production site was investigated.
The amount of water used, the water sinks and the wastewater sources are illustrated
in Fig. 2.
After analysing the process the following common sense measures have been
directly realised which in some cases had a significant effect in wastewater reduction:

. Change of the CIP regime in the production of conditioners: The plant is now
only cleansed when a change to a ‘white product’ occurs (this measure results in a
80% decrease of conditioner CIP wastewater). Verified experimentally.
. Implementation of conductivity sensors in the CIP wastewater system to control
the length of the cleaning cycle. Verified experimentally.
. Modification of the CIP-procedure recipe considering different product viscos-
ities. Verified experimentally.

Fig. 2. Sankey diagram of the water network of the liquid detergent production (data from 1999, the
stream diameters are proportional to the corresponding amounts).
220 B. Goers et al. / Resources, Conservation and Recycling 37 (2003) 217 /226

. Optimisation of the production schedule (avoid/minimise intermediate storage of

products and pre-products from the batch plants).

For the identification of possible sinks for recycle water the constraints concerning
the permitted concentrations of organic and inorganic components have to be
defined by the plant operator. This often turns out to be a difficult task because for
reasons of quality most of the recycle sinks available can not be utilised and reduce
the degree of freedom for network optimisation drastically. In many theoretical
studies this problem is neglected.

3. Development of process options

The generation of process options is the next step. It has to be considered that
during process option generation usually split factor models are used for the
separation/regeneration units as it is done in the water pinch theory and therefore is
supposed to be independent of the choice of unit operations.
Most of the water demand of this site is used for the production water for the
detergent liquid (Fig. 2). No recycle water is allowed to be used here. The disposals
of the CIP wastewater batches with high loads of detergent products are economic-
ally the most important streams. This CIP water subsystem is the most interesting for
the implementation of regeneration-recycle loops. The surfactants are the key
components in these streams; additional components are dyes, salts, ethanol and
other additives.
Based on this consideration the streams to be regenerated (CIP wastewaters), the
demands on the regeneration process and the possible sinks for recycle loops (first
CIP procedure, soft water supply, sewer) can be identified. Therefore the reduced

Fig. 3. Simplified water network in the liquid detergent plant with possible regeneration recycle loops.
 B. Goers et al. / Resources, Conservation and Recycling 37 (2003) 217 /226 221

network given in Fig. 3 has been identified to be the most relevant for retrofit
activity.

4. Selection of feasible unit-operations

The separation efficiencies, water conversion factors and qualities of the purified
water differ for the different treatment processes. Additionally the non-linear
dependencies on operation parameters and concentrations of components force
the use of complex process models.
Once a regeneration target is determined a feasible unit-operation has to be
identified. The first step usually is based on heuristics (Belhateche, 1995; Grund,
1998). Information about driving force, capacity and restrictions to specific
compounds of the wastewater has to be considered. In some cases unit operations
can be combined in order to take advantage of the performance of coupled units.
The key species in the CIP wastewater are basically surfactants. Auxiliary
substances like salts, dyes, perfumes, ethanol and others only can be found in low
concentrations. The organic load of the CIP wastewater varies in the range of 60 /
120 kg COD/m3. As it was found in the experiments a prefiltration is recommended.
For the separation of surfactants from aqueous solutions the following feasible unit
operations are given in literature:

. Ultrafiltration (UF) for the retention of surfactant micelles (Akay and Wakeman,
1993)
. Nanofiltration (NF) for the retention of surfactant monomers (Goers and Wozny,
2000)
. Fixed bed adsorbers (Dabiri et al., 2000)
. Foam fractionation (Tharapiwattananon et al., 1996; Morgan and Wiesmann,
2001)
. Biological degradation (Schreiner et al., 1999)

Foam fractionation, chemical precipitation and adsorption can be precluded due

to the high feed loads. The biological treatment produces high amounts of sludge for
the same reason but the operation is inexpensive. For the sludge separation, a
secondary treatment system has to be implemented. The membrane systems work
with a water conversion factor of about 80 /90% even for the high feed
concentrations. The NF produces a pure uncoloured permeate but the energy
consumption and total surface area demand are higher than for the UF system.
A feasible combination, e.g. is the reduction of the organic load of the water
stream with an UF process and an additional biological treatment of the permeates
(Schreiner et al., 2002). Another option is the separation of the water with a NF step
and a following enrichment of the retentate with UF. Both schemes are shown in
Fig. 4.
The combination of UF and secondary treatment of the UF permeates by NF was
also investigated but identified as economically worse solution and therefore is not
222 B. Goers et al. / Resources, Conservation and Recycling 37 (2003) 217 /226

Fig. 4. Feasible process options for the treatment of the CIP wastewater.

regarded here. The recycle stream usually has to be disinfected (e.g. electrochemical
disinfection or ozonation).

5. Process and cost modelling

As it was derived before, UF and NF and their combination with biological

treatment where chosen as feasible unit operations for the treatment of CIP
wastewater. For both membrane unit operations, mathematical models describing
the surfactant separation characteristic have been developed. The surfactant UF is
modelled with a gel polarisation model approach (Goers and Wozny, 2000). The NF
separation is modelled with an extended solution diffusion model, which also
considers convective transport of the solute (Brettschneider et al., 2001). Both
models have been verified with experimental data.
To determine the model parameters for new detergent solutions, few standard
experimental investigations have to be carried out (e.g. a water and a batch
experiment with pressure variation). The result is a database for the surfactant
separation, which is the key component in the CIP wastewater stream.
In the common solution diffusion model only the concentration difference of the
solute is the driving force for mass transfer. The transmembrane flux Js,Diff is
calculated with the equation:
Js;Diff B i × (cR cP ) (1)
All measurements with NF membranes have shown an additional term depending
on the solvent flux in the solute transport at constant concentration difference
between retentate and permeate Dc /cR/cP. Concentration polarisation has been
 B. Goers et al. / Resources, Conservation and Recycling 37 (2003) 217 /226 223

neglected. The experimental solute flux Js:

Js cP × JV (2)
can not be predicted by Eq. (1). This effect also has been observed by Van der Horst
et al. (1995). It can be derived from the extended Nernst/Planck equation assuming
shear-induced solute transport. The total solute flux Js can be described by:
Js Js;Diff
Js;V (3)
with the explicit terms:
Js B i ×Dc
JV [cR × (1Rc;i )] (4)
The second term shows an analogy to the porous membrane solute flux. The
parameter Rc,i can be interpreted as a rejection coefficient. Both Bi and Rc,i are
binary membrane-solute specific parameters which have been found constant for the
whole range of concentration, transmembrane pressure and cross-flow velocity
variations. The parameters are normalised to a reference value to get a systematic
possibility of comparing them for different media. The reference values are
determined from the standard NF membrane screening substance MgSO4 (Table
1). Both models (UF/NF) have been validated with experimental data of eight
different surfactant solutions for four different ultrafiltration and nanofiltration
membranes.
In addition to the key component experiments, a screening with detergent
solutions has been made (Fig. 5). The results show a general problem of using
blackbox or simplified models in the design of water networks. The problem is the
difference in driving forces for the different contamination species in the water
stream for one separation process. When regarding the surfactant concentration
(displayed in measures of DOC, dissolved organic carbon), a significant improve-
ment in rejection can be achieved from UF to NF. But in the same range, the total
DOC value is not significantly lowered. The reason for this observation is the
ethanol, which is part of the detergent formulation. Dissolved in water, ethanol
cannot be separated with an NF membrane process (the rest of DOC remains nearly
constant, Fig. 5).
The feasibility of the process now depends on the objective. If a surfactant
separation and recovery is needed, the problem can be solved. If the objective is to
reduce the total DOC to avoid biological degradation processes in the water
consuming processes, another unit operation has to be used. Additionally to the
surfactants and the ethanol, the dyes (decolourisation), the perfumes (inodorous-

Table 1
Normalised binary model parameters for different CIP water solutes

Solute NaCl SDS SDES ABS

Bi/BMgSO4 (diffusive transport) 272 49.4 0.2 0.6

(1/Rc,i)/(1/Rc,MgSO4) (convective transport) 81 7.0 0.7 3.9

Membrane: Osmonics Desal D5K. The reference values are the parameters for MgSO4.
224 B. Goers et al. / Resources, Conservation and Recycling 37 (2003) 217 /226

Fig. 5. Membrane screening results for a detergent CIP-wastewater (detergent 1:9 dilution) with different
UF and NF membranes. The experiments were performed at T/25 8C and constant permeate flux
(adjusted by transmembrane pressure). The mean non-surfactant DOC is about constant.

ness) and the salts (solubility, etc.) have to be considered in the model, too. This
example illustrates the importance of a common wastewater data model. This
database must be compatible to the predictive multi-component model approach for
the unit operations. And additional problem is, that such a model is often not
available or has to be developed (as shown in this study).
The costs are modelled via the calculation of capital values for the process options
(operational costs and capital costs). Expenses for streams going over the treatment
system boundaries (concentrate disposal, rest DOC load of recycle water, etc.) are
considered in the operational costs.

6. Retrofit network analysis and optimisation

For the model-based optimisation, two different methods have been used. The
membrane unit itself has been optimised by a MINLP algorithm (number of stages,
permeate recycles, operation parameters, Beuster et al., 2000). The membrane unit
then was coupled with a model of a biological treatment step (Schreiner et al., 2002).
For three process options the operation parameters again were optimised with an
SQP algorithm. The options have been:

. Three stage membrane system: NF/UF/UF (cascade of feed and bleed stages) with
recycle of the disinfected NF permeate to the process (Fig. 4, top).
. Three steps UF cascade (feed and bleed) with biological treatment of the UF
permeates.
 B. Goers et al. / Resources, Conservation and Recycling 37 (2003) 217 /226 225

. Three steps UF cascade (feed and bleed) with biological treatment of the UF
permeates and recycle of the disinfected effluent stream to the process (Fig. 4,
bottom).

In both cases, the costs for the concentrate stream have been assumed to be zero.
The design solution is very sensitive to this parameter. The capital values for the
process options where calculated for different discounting periods (Fig. 6). As it can
be seen, the alternative with biological treatment and recycle is the best economic
option in the long run. The reason is that despite of the higher capital costs
compared to the NF/UF process the lower energy consumption (low pressure UF at
4 bar) brings an economic benefit as well as the fact that the DOC cannot be reduced
far enough by the NF process. From other calculations with different economic
constraints the conclusion can be drawn, that the optimum process scheme varies
with the cost factors for the product streams (disposal of concentrate, product
recovery, energy costs).

7. Conclusions and outlook

For a systematic retrofit design of industrial process water systems a systematic

model based approach was presented. By using model-based methods in the design
and synthesis of water and wastewater systems one faces the problem of a much
more complex component mixture and the lack of a common data model what is
state of the art in the design of chemical processes. This fact has the following
implications:
The selection and consideration of all relevant key components in the first design
steps (data acquisition and process option generation) is very important. The
relevance is not limited to load and legal restraints, interactions with the capacity
and selectivity of regeneration process devices have to be taken into consideration.
The reuse of regenerated water often is strictly restricted by the operators even when

Fig. 6. Capital values for the different process options for different discounting periods n .
226 B. Goers et al. / Resources, Conservation and Recycling 37 (2003) 217 /226

the feasibility is proved by investigation (risk of cross-contamination). Experimental

verification of the regeneration process units is strongly recommended and cannot be
neglected for the verification of the theoretical results.
For future developments a common data model for industrial wastewater streams
would allow model-based optimisation, as it is state of the art in the field of chemical
process design. Such a model has to be developed also to facilitate the integration of
models from different developers or tools.

Acknowledgements

Financial support for this project by the German Research Foundation DFG is
gratefully acknowledged.

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