Desalination 189 (2006) 5358

First operating experience with the treatment of 3,100 m3/h of Elbe River water by means of reverse osmosis to produce process water and demineralised water for use in the pulp industry
U. Kremser*, G. Drescher, S. Otto, V. Recknagel
Linde-KCA-Dresden GmbH, Bodenbacher Str. 80, 01277 Dresden, Germany Tel. +49 (351) 2503374; Fax +49 (351) 2504826; email: ulrich.kremser@linde-kca.com

Received 20 April 2005; accepted 25 June 2005

Abstract In early 2002, Linde-KCA-Dresden GmbH received an order from RWE Industrie- Lsungen GmbH for the construction of a water treatment plant for the Stendal Pulp Mill at Arneburg near Stendal (Germany). Within the scope of the project one of the largest water treatment plants based on the reverse osmosis process in Europe was built and commissioned in the years 2003 and 2004. The water treatment plant operating since January 2004 has been capable of meeting the process water requirements of the Stendal pulp mill from the time of its commission. Differences in the quality of the water taken from the Elbe river which are due to season and weather conditions are compensated for by a pre-treatment system. The water supplied to the reverse osmosis system meets the required good quality standards. During the first year of operation, the output of the reverse osmosis membranes was found to decrease. It was possible by cleaning the membranes to achieve a complete or at least partial restoration of the original flow. Keywords: Reverse osmosis; Pulp industry; River water

1. Introduction The production of pulp requires a considerable amount of process water of an exactly specified
*Corresponding author.

quality to ensure that the final product meets the desired purity requirements (Table 1). In early 2002, Linde-KCA-Dresden GmbH received an order from RWE Industrie-Lsungen GmbH for the construction of a water treatment

Presented at the 10th Aachen Membrane Colloquium, 1617 March 2005, Aachen, Germany. 0011-9164/06/$ See front matter 2006 Elsevier B.V. All rights reserved
doi:10.1016/j.desal.2005.06+.012

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Table 1 Quality of raw water and required product water qualities

Raw water (River Elbe) pH Conductivity, S/cm Suspended solids, mg/l COD, mg/l DOC, mg/l TOC, mg/l AOX, mg/l Ca2+, mg/l Mg2+, mg/l Na+, mg/l K+, mg/l Cl, mg/l NO3 , mg/l 2 SO4 , mg/l SiO2, mg/l HCO3 , mg/l TDS, mg/l Process water TH (CaCO3), mg/l TDS, mg/l Turbidity, NTU Colour, Pt Co Alkalinity (CaCO3), mg/l Fe, mg/l Mn, mg/l SiO2, mg/l Free CO2, mg/l Cl, mg/l Demineralized water Conductivity, S/cm SiO2, g/l TOC, mg/l Na+ and K+, g/l

7.29.2 1.430 60 41 6.7 13.0 0.052 130.0 23.6 124.6 11.0 252 25.0 185.1 12.9 152.5 917 85 250 <1 <5 <75 <0.1 <0.05 <20 <10 <200 <0.2 <15 <0.2 <20

Raw water is taken from the Elbe River (Table 1) at a rate of about 3,100 m/h which is turned into 2,200 m/h f process water and 300 m/h of demineralised water. Additional 400 m/h of process and turbine condensates are cleaned. 2. Process flow The layout of the process is as follows (Fig. 1): The water is taken in from the Elbe river through an intake structure. After the water has passed one sand separator and pre-filters with a filter mesh size of 200 m it is heated to a temperature of 2025C by means of plate-type heat exchangers. This is followed by a chemical physical treatment stage in which metered amounts of a ferric chloride are added to bind the substances suspended in the water and remove part of the organic constituents. The sludge produced by this process is settled down by sedimentation and passed on to the in-plant sludge dewatering system. The remaining un-dissolved substances are removed in filtration stages, i.e. sand filters and 5 m cartridge filters. The water treated in this way is now largely demineralised in a reverse osmosis process. This system is composed of four parallel lines which are each fed by their own high-pressure pump. Three lines are subdivided into two sections with 55 pressure vessels each. Each pressure vessel contains seven reverse osmosis membrane elements. The fourth line contains only one section which provides reserve capacity for extension at a future stage. This subdivision into sections ensures a high availability, if single sections are out of operation for cleaning work or membrane replacement. The permeate is mixed with filtered water to ensure that the desired quality parameters are met. Part of the permeate (300 m/h) is fully demineralised in a multi-step filter system using ion exchangers and is used subsequently as boiler feed water.

plant; a report on this project was published in 2003 [1]. Within the scope of the project, one of the largest water treatment plants based on the reverse osmosis process in Europe was built and commissioned at Arneburg near Stendal in the years 2003 and 2004. The plant has since provided process water and fully demineralised water for a number of production usage points.

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River Water 3100 m3/h

55

Coarse Screen

Grid Separator

Sand Pre- Filter Raw Condensate 400 m3/h

Heat
Exchanger

Heat FeCl3 NaOH FHM

Exchanger

Coagulation Backwash Water Sedimentation Sludge H2SO4 NaOH Mixed Bed Regenerant Cartridge Filter

Backwash Water

Filtration Condensate 400 m3/h

Backwash Water

Cartridge Filter H2SO4 NaOH Reverse Osmosis CO2Degasser Multistep Filter

NaHSO3 Antiscalant Antifoulant

Regenerant

Process Water 2200 m3/h

Demin Water 300 m/h

Fig. 1. Process block diagram.

3. Pilot tests The treatment of surface water normally makes particularly high demands on the treatment process because surface waters vary greatly in quality.

This is evident by differences between the seasons of the year, e.g. summer and winter or after periods of heavy rainfall. In this respect, the water taken from the Elbe River certainly ranks among those difficult to treat.

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A decision was taken for this reason to make pilot tests simultaneously with the engineering and construction of the plant in an effort to collect data and gain experience even before the commissioning of the plant. Also extensive JAR tests were made during the pilot testing phase. An important result of the tests was the determination of the quantity of ferric chloride to be added for the destabilization of the Elbe water at the stage of pre-treatment (Fig. 2). Thus, it is necessary for achieving an optimum result of the precipitation/flocculation process to add FeCl3 at a rate of 6080 mg/l. This result could be verified by the later operation of the large-scale plant. Furthermore, great variations were found in the selection of a suitable flocculating agent (polymer). Slight variations in composition, molecular weight and charge already lead to great differences in the quality of the cleaned Elbe water (Fig. 3). Because of the fluctuations in water quality, it is necessary to make JAR tests at regular intervals simultaneously with the operation of the large-scale plant to ensure the optimum adjustment of the plant. Fig. 4 shows the results of the reverse osmosis operation during the pilot test. The values norm-

Fig. 2. Optimum quantity of ferric chloride.

Fig. 3. Behaviour of different polymers.

Fig.4. Normalised permeate flow pilot plant.

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alised with respect to temperature and pressure, have an almost constant behaviour over the entire period of operation. After about 400 h of operation, two membrane elements were removed from the pilot plant to change the flow velocity and allow a different permeate recovery.

4. Results for the large-scale plant After RWE had completed the erection work the plant was commissioned under actual operating conditions as of January 2004. Beginning with the pre-treatment stage, the commissioning procedure was continued by putting the lines of the reverse osmosis system into operation one after the other. Actual operating conditions had to be taken into account, such as the supply of the water generated to user processes and the discharge of waste water because the pulp mill was not yet in operation at that stage. Fig. 5 shows the operation of two reverse osmosis lines by reference to permeate flows normalised with respect to pressure and temperature. In addition, the temperature of the raw water is shown. It is obvious that despite the standard-

isation, the values are to some degree dependent on temperature. It can be gathered from the curves that despite the conditions being identical in other ways there are differences in the operating behaviour of single lines which are conducive to varying behaviour of the membranes. For example, line 2 (rack 2) shows a steady decrease of the normalised values from the beginning. Line 7 starts with a low flow but arrives at an approximately constant rate over a period of 1,500 h of operation until the end of June. Also, the flow is not withdrawn at a uniform rate. On closer investigation of the membranes after their autopsy by visual and radiographic methods, it was possible to exclude biofouling or scaling as causes. Extensive cleaning efforts in the period between the beginning of October and the end of December using different detergents have shown that there are several ways of cleaning the membranes which partly result in a complete restoration of the permeate flow or at least in a considerable increase. Since the beginning of 2005 after optimized cleaning procedures had been applied, a nearly constant flow of all racks has been established.

Fig. 5. Operating curves (normalized permeate flow, temperature).

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Further investigations for finding the causes of the initial flux decline are in progress at the time of publishing this report. Regarding the water quality achieved, it has been established after a period of running-in that salt is removed at a constant rate. The normalised salt retention is 98.6% on average and is thus higher than the design salt retention of 98.4%. The

permeate conductivity levels are in the order of magnitude of 15 S/cm (Fig. 6). References
[1] U. Kremser and W. Dreyer, Aufbereitung von 3.100 m/h Elbewasser zu Prozesswasser und vollentsalztem Wasser fr die Zellstoffindustrie mittels Umkehrosmose, AMK 2003 (in German).

Fig. 6. Permeate quality.

Fig. 7. Partial view of the Lamella clarifier.

Fig. 8. Reverse osmosis racks.