MEMBRANE TECHNOLOGY IN WATER TREATMENT APPLICATIONS

Wolfgang M. Samhaber, Institute of Process Engineering, Johannes Kepler University Linz; A-4060 Leonding, Welser Strae 42 Bernhard Haschek, EVN Water, A- 2344 Maria Enzersdorf, EVN-Platz Abstract Drinking water and pure water are an increasingly limited resource and billions of people are living already today with shortages or with an inadequate access to clean water [1]. In many countries available water sources can not be used straight from surface water or from sub-surface water or ground water. In contrast to those regions the quality of fresh water resources in Austria exhibits an excellent standard, because most of the water is based on deep ground water sources. Beside of this great extend of best quality water sources there are certain areas, which have some requirements of treatment to get the accustomed high quality drinking water. The aim of the field test investigation was to evaluate the conceptional design of a ground water treatment process, which can be operated on a low energy basis without a need of antiscalants and frequent acidic flushing. The ground water source for this study was characterized by a high degree of hardness and nitrate content close to the upper regulation limit. The requirement therefore is a strictly controlled degree of the hardness on the retentate side which should not exceed a maximum limit of 80 dH. The combination of NF and RO membrane types has proven advantageous in the field tests concerning the given targets. The NF membrane contributes in the softening and in a major flow yield parallel to a small nitrate reduction. The RO membrane again takes care among others of nitrate reduction and of course to a complete hardness reduction too. The combination of both membrane types shows an appropriate way to produce high quality water. In a field test study practical data and long-term test experiences have been collected and some of it will be presented in this paper. The field tests were established and focused at the water sources of EVN Water in Bisamberg, located north-west of Vienna. KEYWORDS Water treatment, nanofiltration, reverse osmosis, EVN Bisamberg

1. Introduction Since the beginning of the membrane technique RO membranes and later also NF membranes are used to produce high quality water from different sources like sea water, and brackish water [2], surface water, secondary treated effluent and in certain aereas and local situation sub-surface or ground water. Water contains beside of the necessary dissolved matters suspended and dissolved impurities. The water sources often bear disease causing bacteria, viruses, and parasites and this water must be treated and purified to meet human needs. Chemical disinfection is in wide use to treat water but disinfection forms again disinfection by-products (DBP). To avoid the generation of such DBPs it is necessary to remove natural organic matters efficiently prior to disinfection. Pesticides and nitrates in ground water is a growing problem in agricultural areas [3]. Beside of flocculatio, coagulation and clarification membranes have demonstrated excellent results in natural organic matter separation and have gained a high potential in future in the production of drinking water.
ions, salts Ca, Mg, carbonate colloidal Viruses NOMs
0,1 nm 1 nm 10 nm 0,1 m 1 m

dead-end filtration
suspended solids microorganisms protozoas
10 m 100 m

RO UF- MF NF
Fig. 1: Membrane application in the different water treatment areas The major fields of membrane applications are in the treatment of different sources of water and are shown in Fig.1. Membrane and membrane processes are generally alternative ways to conventional techniques and it should be noted to choose the classical way when ever this is technically and economically possible. Membrane processes are combined with a relevant demand for electrical energy. The minimization of the energy demand of water treatment systems is an important task facing our future water resources [4]. Membrane processes need hydraulic pressure to force water through a semi-permeable membrane which needs energy and if we are speaking of energy, we have to face the mass of CO2 which is emitted therefore to get water in defined quality. If we count the quantity of CO2 which we will emit to produce softwater out of ground water, we have to realize that we are emitting between 200 to 500 g CO2 per produced 1000 l of product water. Its a relatively wide CO2 emission range which is a result of different process parameters and of the feed water quality. 2

However membranes are applicable for water sources which cannot be treated anymore successfully by e.g. convetional techniques combined with disinfection chemicals. Membranes exhibit the ability to reject most contaminants and have attained for these tasks a high acceptance in the last 20 to 30 years and many membrane applications in water treatment have been realized therefore and devepment of economically and ecologically processes is needed [5]. In the water industry there have been collected parallel to this development experienced ways of operations in the treatment of different water sources. The scale of application of membrane plants has grown as well and the sizes of membrane plants will have further more a rising demand for developments to eneable the purifying water in areas where water is available but the quality for human consumption is not given. The challenge to apply membrane processes for the different raw water qualities is to make these techniques applicable in respect to specific plant and energy costs. Certain plant concepts and process combinations are inevitable to meet these designated targets and some of them will be presented in this paper and practical experiences from field tests discussed. Variations of this technology include reverse osmosis (RO), nanofilitration or low pressure RO, ultrafiltration and microfiltration. As membrane plants need energy it is crucial to minimize the energy consumption for this fast growing demand in water treatment applications also in view of climate change emission reduction. 2. Aim of field test investigations The purification of water with less energy costs and minimum use of chemicals and minimizing the impact on the environment have been specified for objective targets parallel to a major reduction of nitrate content with an accompanying softening process. The treatment plant is foreseen to be built in Bisamberg in 2012 and the total final capacity of available ground water treatment will be about 1000 m3/h. 2.1 Raw water quality The feed water quality is to be seen from Table 1 which contains the total hardness (GH) instead of mg/l in degree of German Hardness [dH].
Content mg/l Averages Ca 129 Mg 71 GH 35 Na 35 K 8 Cl 90 NO3 53 SO4 184 HCO3 395

Tab.1: Raw water composition of the feed well water 2.2 Pilot plant The field tests were carried out form July 2009 until August 2010. During this time the pilot plant was operated 24 hours/d and 7 days per week continuousely. To avoid a possible fouling a Bio-Cel filter was used at the beginning, but by-passed after a period of 4 months to find out if cartridge filters (5m and/or 1m) are appropriate and operable for taking care of suspended solids in the up-stream side of the pilot plant. The replacement of cartridge filter period was about 3 months due to small amounts of iron in the feed, which was acceptable for pre-treatment. 3

PDISHL 1.626 TIRSHL 1.624 PIRSH 1.622

FIRCSHL

SIR 1.625 0,9 m3/h 41 % 467 l/h

M 4,8 bar FIR 1.632

ML1 Yield 63 % 174 322 l/h l/h

37 % 5,3 bar FICR 1.628 1.500

1.620 Feed Line 1 M 789 l/h 5,7 bar P 1.1

FIR 1.630 Retentat 293 l/h Drain

Fig. 2: Flow sheet of one membrane separation line of the pilot plant The membrane separation part of the pilot plant consists of two identically and separated lines, each line equipped with two 4040 elements in series. Therefore the treatment was done in two steps per line. As it can be seen from the flow sheet from Fig. 2, the permeate lines of each 4040 element were separated and the samples were taken from each permeate line to enable the evaluation of the combined performance and that for observing the specific contribution of the different membranes within the established separation concept. The instrumentation allow to collect all hydraulic data and they were stored every 10 minutes and it facilitates further the fully automated process. Fig. 4: Pilot plant mounted within a air-conditioned container with all necessary process control items for a fully automated and remote controlled operation 4

2.3 Membranes From the previous laboratory studies the AG (Desal-GE) and NF90 (Dow-FilmTec) were selected, which were well performing in the small scale studies. For that reason it was decided to test on the one hand the membrane types of the lab studies and on the other hand to take over the ESNA1-LF2 (Hydranautics), HL (GE), and the XLE (Dow-FilmTec) types of membrane, which were recommended additionally for the field tests. The element size was 4040 and the membrane area about 85 ft2 (7,9 m2). 3. Results of the pilot tests 3.1 Lessons learned with scaling During the the first weeks of field tests the combination of the evaluated membranes were experienced together with parallel simulation on the basis of the received data. The relatively high hardness brought some uncontrolled scaling problems at the beginning and made shortly certain operational modes necessary to avoid overshooting the CaCO3 solubility limits.
HL4040 ML1.2

HL 4040 ML1.2 (no circulation)

90 80 70 60 50 40 30 20 10

90 80 70 60 50 40 30 20 10
12 16 07 14 19 21 09 00 .0 8. 04 04 .0 8. .0 8. .0 8. .0 8. .0 8. .0 8. .0 8. .0 8. 02

Flux [l/h bar element]

Yield in %

Spec.Flux [l/h bar element]

Yield [%]

31 .0 7. 09 31 .0 7. 12 31 .0 7. 14 31 .0 7. 16 31 .0 7. 19 31 .0 7. 21 01 .0 8. 00 01 .0 8. 02 01 .0 8. 04

03

03

03

T i me

t i me

Fig. 3: Description of the 2nd element (HL) of ML1 with and almost without scaling In Fig. 3 the rapid scaling is demonstrated which was induced by a steady increase of the yield on the left side and on the right by keeping the yield low not to exceed the solubility limit to attain stable conditions. The optimal operating concept could be obtained by a combination of a NF first and a RO type membrane on the second place. With this concept it was possible to achieve 65 to 70 % yield depending on the hardness in the raw water, which varied between 32 and 42 dH. This result was obtained without using any antiscalant in a long-term continuous operation. The crucial hardness which was absolutely to observe was a upper limit in the retentate of 82% based on this specific feed water. A second scaling experience should be additional described, to demonstrate the sensitivity and the dynamic of that system and the affect of available cristallization seeds.

03

03

03

03

It was started with a linear increas of the flow yield which raised the concentration and the hardness during the 22nd of April 10 (see Fig. 4).
HL4040N-Flux vers Yield
0,70 5,00

0,60

4,50

0,40

3,50

0,30

3,00

0,20

Yield

Flux

2,50

0,10 22.04.10

2,00 29.04.10 06.05.10 13.05.10 20.05.10 27.05.10

Fig. 4: Flux effects trough yield increase due to on-going carbonat scaling and regeneration through complete or incomplete acidic flushing After acidic wash, which was very short and uncompleted it can bee seen that the flux is again decreasing despite of a significant reduction of the yield. After a proper flushing the flux rate was recovered and back at the previous level. During the entire time of the field tests the membranes never have seen any antiscalings.
10,0 9,5
Specific Flux [l/m2hbar]

9,0 8,5 8,0 7,5 7,0 6,5 6,0 5,5 5,0 16.05.10 06.06.10 27.06.10
Time

18.07.10

08.08.10

Flux [l/mh bar]

0,50

4,00

YIELD [/]

29.08.10

Fig. 5: Permeate flux of ESNA with a mean flow yield of 41 % (Pos.: ML1.1) In Fig. 5 the specific permeate flux of the ESNA in ML1.1 is shown as a perfect constant flux over the period between May and August. The slight increase of flux over time can be explained by temperature elevation in ground water from 12,5 in May to 14 C with the end of August 10.

3.2 Membrane performance comparison On the collected experiences of the field test the ESNA in connection with the XLE in series have proven its operability for this task. The ESNA is an open NF membrane which exhibits still some percentage points in nitrate retention beside of a very high permability for monovalent ions to pass to the product water, where those ions are needed for the water quality. A comparison of the retention of ESNA and HL for mono- and divalent ions can be drawn on the basis of the calculated data, which were collected during the field tests and are illustrated in Fig. 6. ESNA and HL exhibit almost similar separation performances regarding the depicted ion retentions. The HL membrane indicates just for Mg a higher retention; the other retention values can be considered as a little bit higher of the HL membrane. Beside of the retention coefficients the obtained specific fluxes are determining additional the separation performance.

Fig. 6: Retention of Ca-, Mg-, HCO3-, SO4- and NO3 -ions of measured during the fields of the HL and ESNA membrane The decision between HL and ESNA could be done based on the flux comparison in Fig.7, where the different data of these membranes are plotted. It is evident, that ESNA is better working on a low pressure basis with still quite a significant rejection for divalent species to contribute to softening. The ESNA element has shown a very smooth operation over the whole period of field test time and stable and of course higher fluxes. In connection with the RO step the ESNA type membrane provided a flow yield of about 40 % and hardness reduction down to 20dH without a relevant retention for the monovalent ions. In the combination NF membrane which makes about 40 % yield must be followed by a high selective low pressure RO which produces a proper permeate quality for blending with the NF permeate to get the wanted final quality of the treated water.

600 550 Element flux [l/h] 500 450 400 350 300 250 4,0

HL-ML1.2 Polynomisch (HL-ML1.2)

ESNA-ML1.1 Polynomisch (ESNA-ML1.1)

5,0

6,0

7,0

8,0

9,0

10,0

Operating pressure [bar]

Fig. 7: Element flux of NF-membranes ESNA and HL versus operating pressure

The AG, the NF90 and the XLE were to be evaluated for this purpose. The AG has its strength in the high pressure applications, the NF90 and XLE are low pressure membranes differing in the retention behaviour. In Fig. 8 these diference in retention can be seen and it indicates a similar separation performances of these membranes.

Fig. 8: Comparison of retention between NF90 and XLE The NF90 is known as a dense NF membrane and one can see that the divalent ions point out a comparable retention like it with the RO membrane. The HCO3 retention is similar, the nitrate retention is lower of the NF90. As from the RO part a higher nitrate retention is wanted and the decision for the XLE was drawn based on this relation and on the higher specific flux of the XLE type membrane. To compare finally yet the AG with the XLE the respective retention diagrams are shown in Fig. 9. These two membranes are quite comparable in all there monvalent ions retention coefficients. 8

This coincidence is remarkable, because these membranes are manufactured by different companies and the major difference is an almost 5 fold flux.

Fig. 9: Comparison of AG and XLE regarding the respective retention Another remarkable fact can be shown on the diagram of the XLE membrane, if we comparing the Na- with the NO3-retention. For the simulationof the treatment process the experimental data was used to describe the flux versus retention for the ions of interest. For that purpose the Push model was used and in Fig. 10 some empirical data are shown and the model curve for Na- and nitrate retention. The XLE exhibits a higher selectivity for nitrate as for sodium, which increases the preference of that membrane for the given requirement.
XLE 4040 ML2.2

100 99 98 Rejection in % 97 96 95 94 93 92 0 100 200 300 400 500 Permeate Flux [l/h,Element]

R-NO3 Pusch Model R-Na Pusch-Na-Model

Fig. 10: Na- and NO3-retention of the XLE type membrane

3.3 Energy demands Based on the the hydraulic data, which was collected during the field tests, the energy demand in that pilot scale was calculated. For the efficiency of the pumps a value of 78 % was assumed and power consumption of the feed and circulation pumps were calculated from the respective volume flows of feed and permeate lines. In Fig. 11 those result are plotted versus the applied feed pressure based on a concept with an ESNA in the first stage and a XLE on the 2nd of the retentate side. In that concept two third of the water is produced in the NF-stage and 1 third in the RO stage. For nitrate 50 % reduction was achieved and the hardness were brought to a range between 10 to 12 dH depending on the feed situation.
0,50 0,45 0,40 0,35 0,30 0,25 0,20 4,0 5,0 6,0 7,0 Pressure [bar] 8,0 9,0 10,0

3. Conclusions and discussion

The aim of the field test investigation was to evaluate the conceptional design of a ground water treatment process, which can be operated on a low energy basis without a need of antiscalants and frequent acidic flushing. The ground water source for this study was characterized by a high degree of hardness and nitrate content close to the upper regulation limit. The requirement therefore is a strictly controlled degree of the hardness on the retentate side which should not exceed a maximum limit of 80 dH. The combination of NF and RO membrane types has proven advantageous in the field tests concerning the given targets. The NF membrane contributes in the softening and in a major flow yield parallel to a small nitrate reduction. The RO membrane again takes care among others of nitrate reduction and of course to a complete hardness reduction too. The combination of both membrane types shows an appropriate way to produce high quality water. 10

Energy demand [kW/m ]

References [1] M. A. Shannon, P.W. Bohn, M. Elimelech, J.G. Georgiadis, B.J. Marinas, A.M. Mayes, Science and technology for water purification in the coming decades, Nature 452 (7185) (2008) 301310 [2] Lauren F. Greenlee et. al.; Reverse osmosis desalination: Water sources, technology, and todays challenges: Water research 43 (2009) 2317-2348 [3] Van der Bruggen, B. et. al.; Application of nanofiltration for removal of pesticides, nitrate and hardness from ground water: rejection properties and economic evaluation: Journal of Membrane Science 193 (2001) 239248 [4] Asmerom M. Gilau, Mitchell J. Small; Designing cost-effective seawater reverse osmosis system under optimal energy options: Renewable Energy 33 (2008) 617 630 [5] Tansel Berrin, New Technologies for Water and Wastewater Treatment: A Survey of Recent Patents: Recent Patents on Chemical Engineering, 2008, 1, 17-26

11