Desalination 167 (2004) 209216

Effects of the chemical injection points in pre-treatment on reverse osmosis (RO) plant performance
M. Hafsi*, A. Khaoua, S. Ben Abdellah, M. El Mghari Tabib
Direction Contrle de la Qualit des Eaux, Station de Traitement, avenue Oued Akrach, BP Rabat Chellah,10002 Rabat, Maroc Tel. +212 (7) 759600; Fax +212 (7) 752377; email: onepdlq@onep.ma

Received 5 March 2004; accepted 15 March 2004

Abstract Good characterization of raw water quality and subsequent identification of the most appropriate pre-treatment are not sufficient to ensure successful functioning of a reverse osmosis plant. The Tan Tan demineralization plant was set up in July 2003 for 20 l/s production capacity. The brackish water with total dissolved salt (TDS) of 3 ppm is supplied from Khang Lahmam underground water located 70 km from the plant. Since it started working, the main problem encountered in the Tan Tan demineralization plant was the continuous presence of a membrane biofouling problem which provokes high pressure drop values and requires an increased washing frequency, as often as twice a month. The diagnosis undertaken to remedy this anomaly has concerned all the pre-treatment steps including the raw water, quality of the applied chemical reagent types and concentrations, and the composition of the biofilm. Collected data confirm the good raw water quality specially the absence of heterotrophic bacterium (aerobic-anaerobic analyzed at 37C+1C and to 22C+1C) and low oxydation values (<3 ppm). Chlorine-raw water contact time, about 17 h, is largely sufficient to insure its efficiency. Analyses of the biofilm have shown the abundance of heterotrophic germs Pseudomonas sp. and ferobacter absence despite the reddish color of the biofilm. The hypothesis retained to interpret the origin of the biofouling is the sodium bisulfate injection point, upstream of the microfilter. The microfilter then plays the role of a bioreactor favoring a bacterial proliferation upstream of the membranes. The simple displacement of the injection point of that of sodium bisulfate will allow remedying definitively the disorder caused by frequent appearance of biofouling. The present article, through the analysis of operational data, and particularly of results and actions undertaken, focuses on the crucial role of reagent injection point in optimization of reverse osmosis plant operation. Keywords: Demineralization; Biofouling; Biofilm; Appropriate pre-treatment *Corresponding author.
Presented at the EuroMed 2004 conference on Desalination Strategies in South Mediterranean Countries: Cooperation between Mediterranean Countries of Europe and the Southern Rim of the Mediterranean. Sponsored by the European Desalination Society and Office National de lEau Potable, Marrakech, Morocco, 30 May2 June, 2004. 0011-9164/04/$ See front matter 2004 Elsevier B.V. All rights reserved

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1. Introduction The reverse osmosis Tan Tan demineralization plant began operations in July 2003, to reinforce the drinking water supply of Tan Tan and neighboring communities. Endowed with production capacity of 20 l/s, the plant is supplied with brackish water from Khang Lahmam under ground water having a salinity of about 3 g/l. Since its start-up, the operation of this plant was confronted with a semi-permanent presence of the biofouling phenomenon which increases membrane pressure drop. The first consequence was the very high frequency of cleaning, as often as twice per month. 2. Description of the plant 2.1. Raw water characterization The raw water to treat is characterized by a total dissolved solids (TDS) of about 3300 ppm, good bacteriological quality and a very low organic content (<3 ppm). The mixture and pre-

chlorination of water of three boreholes are made in a reservoir located at Zaouia to approximately 80 km from the plant. 2.2. Presentation of pre-treatment The pre-treatment was designed to improve the raw water quality, and to conform the pre-treated water with the reverse osmosis membranes requirements. It includes the steps shown in Fig. 1. Chlorine injection in the raw water is done 80 km upstream of the demineralization plant. About 17 h is approximately the contact time duration between chlorine and raw water. It is designed to inhibit any bacterial proliferation, able to generate the formation of a biofilm, and if necessary to oxidize any manganese and iron trace in raw water. 2.2.1. Acidification Sulphuric acid was injected to prevent calcium or carbonate scaling and to adjust pH to pH 6.9.

Prechlorination H2SO4

Borehole Raw water reservoir

Borehole

Antiscalan

SBS

Borehole

NaOH

Microfilter Line 1 Treated water reservoir CaOCl2 Brine

Sand filter

By-passed brackish water

Fig. 1. Schematic presentation of the Tan Tan demineralization plant.

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2.2.2. Sand filtration Sand filtration is done by two high pressure vertical filters (one filter per line) filled with sand with a diameter of about 1 mm, to retain the suspended solids that might be present. The speed of filtration is 10 m3/m2.h. 2.2.3. Antiscalant injection Injection of antiscalant agent (Flocon 260) upstream of the microfilters ensures the inhibition of sulphate salt and iron scaling at the membranes. Sodium bisulfate and microfiltration: pretreated water dechlorination is attained by Sodium bisulfate (SBS) injection at the entry of the microfilters, which are the ultimate protection of the membranes against any suspended matter. 2.3. Reverse osmosis stack The reverse osmosis plant production capacity is 1740 m3/d with a TDS <500 ppm. The total production is assured by thirty-six membranes of type Filmtec BWLE 440 DOW. There are disposed in brine-staging configuration. The conversion ratio is about 6769%. Both lines 1 and 2 are laid out in parallel and operate under the same conditions. 2.4. Post-treatment The post-treatment of produced water to reestablish its calco-carbonic equilibrium is ensured in two steps: Mixture of the membrane produced water with an equivalent quantity of brackish water pH adjustment by sodium hydroxide injection The treated water quality has to respect the following conditions: Saturation ratio of 1.21.5 Saturation index of 0.10.3 Ca2+ of 8F (<32 ppm) pH<8.2

This water was disinfected by calcium hypochlorite injection. 3. Analysis of working conditions In order to optimize the working of the reverse osmosis Tan Tan plant, checks of the water quality, pre-treatment and physical parameters of operation (flow, pressure) were established. Water conductivity, water flow, and membranes pressure drop was continuously controlled. Initially, the measured values for these three parameters were respectively 39 m3/h, 70 .s/cm, 2.0 bar in the first stage and 1.2 bar in the second. After approximately one month of working, it was noticed: The pressure drop increased to 2.2 bar at the level of the first stage (line 1). The pressure drop at the level of the second stage, quality and total quantity remained stable. One month later the continuous increase of pressure reached the threshold limit value (3.1 bar) which causes shut down of the plant. Inspection of the equipment upstream of the reverse osmosis membranes showed the presence of gelatinous substance, specific to biofilm development. To overcome this abnormality, it was decided to examine how to remove the biofilm and how to remedy definitely to the origin of this disorder. Two actions were undertaken: Chemical cleaning using sodium hydroxide at 0.2% by recirculation during 5 h, then rinsing with produced water To re-establish the prechlorination, first by applying the chlorination shock at 3 ppm to disinfect the system from the chlorine injection point to the high pressure pump, about 80 km. Then applying the raw water chlorine demand, 0.6 ppm, was adopted. The residual chlorine obtained at the entry of the plant was about 0.4 ppm, after about 17 h waterchlorine contact time.

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3.1. Observation of disorder Figs. 2 and 3 give the pressure drop evolution over four months. Line 1: The evolution of pressure drop at the first stage showed that after approximately a month, an abrupt increase was measured as indicated before. Approximately a month of exploitation after this first fouling a second increase was noted to reach the automatic threshold lately pressure drop evolution regulated at 3.5 bar, thus indicating the second fouling. In detail examination of the profile shows an exponential tendency.
4

Line 2: A continuous increase of the pressure drop was noted in the first stage without reaching the maximum automatic threshold limit value. However, during all this period, the pressure drop remained practically constant (1.4 bar) in the second stage. Having regarded the evolution of the pressure drops and visual observations it was possible to confirm that the origin of the observed disorder is the membrane biofouling: Inspection of the equipment upstream of the membranes revealed abundant gelatinous matter.

Differential pressure (bar)

3.5 3 2.5 2 1.5 1 0.5 0 8/7/2003 8/14/2003 8/21/2003 8/28/2003 9/4/2003 9/11/2003 9/18/2003 9/25/2003 10/2/2003 10/9/2003

1st stage

2nd stage

Date

Fig. 2.Line 1: profile of the pressure drop evolution.

3.5 3 2.5 2 1.5 1 0.5 0

9/ 20 03 0/ 20 03 1/ 20 03 9/ 1/ 20 03 9/ 2/ 20 03 9/ 3/ 20 03 9/ 4/ 20 03 9/ 5/ 20 03 7/ 20 03 8/ 20 03

1st stage

Differential pressure (bar)

Differential pressure (bar)

4 3.5 3 2.5 2 1.5 1 0.5 0

1/ 20 03 10 /2 /2 00 3 10 /3 /2 00 3 10 /4 /2 00 3 10 /5 /2 00 3 10 /6 /2 00 3 10 /7 /2 00 3

1st stage

2nd stage

2nd stage

8/ 2

8/ 3

Fig. 3. Line 1: detail of pressure drop evolution showing the exponential profile.

8/ 2

8/ 2

8/ 3

10 /

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Only the first stage was affected by the pressure

drop increasing, with a typical exponential form, specific to the consequences of the bacterial proliferation. The presence of the salt crystals in the second stage argues in favor of mineral fouling.

+1C), an abundance of common heterotrophic germs: Pseudomonas sp., and an absence of ferruginous bacteria, in spite of the reddish color of the biofilm. 4.2. Optimization of the pre-treatment The development of the biofilm in spite of the presence of prechlorination can be explained only by bacterial proliferation after the chlorine neutralization by sodium bisulfate injection. This is perfectly in concordance with former studies which attronite the phenomenon to a bacterial resistance to chlorine. Indeed, the rare bacteria, initially present naturally in water, could resist the remnant effect of chlorine, then after neutralization of the chlorine by SBS, a very important development happened on the microfilters which were used as support for the biological increase activity. To overcome this abnormal situation, the SBS injection point was moved from upstream to downstream of the microfilters. An immediate effect on the pressure drop on the level of microfilters was measured as given in Fig. 4. To explain these results other chemical analysis consisting of total organic carbon measure were conducted. Results are given in Table 2.
Displacement of SBS injection point

4. Actions undertaken To remedy the disorder, some actions were undertaken to identify the biofilm origin and composition, to remove it, thereafter to adopt the appropriate modification in the pre-treatment. 4.1. Analysis of biofilm composition The bacteriological analysis of the biofilm (Table 1), carried out respectively by the Central Water Quality Control Laboratory (ONEP) and the Brest Ocean Laboratory (France), revealed an absence of heterotrophic bacterium (aerobic anaerobic analyzed at 37C+1C and to 22C
Table 1 Bacteriological characterization of the biofilm

Microorganisms at 22C, 68 h Microorganisms at 36C, 44 h

>3 e+007 n/ml >3 e+007 n/ml

Differential pressure (bar)

1.2 1 0.8 0.6 0.4 0.2 0

SKID I

SKID II

10H0022H0010H0022H0010H0022H0010H00 22H0010H0022H0010H0022H0010H0022H00 3/12 4/12 5/12 6/12 7/12 8/12 9/12

Dates

Fig. 4. Microfilters pressure drop profile evolution.

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Table 2 Total organic carbon evolution at different pre-treatment step

Sampling point Raw water Filtered water, SF Filtered water, F Produced water Produced water

Total organic carbon, ppm Before the modification of the injection point* 0.4 0.3 0.5 After the modification of the injection point** 0.89 1.33 0.75 0.49 0.54

*Prechlorinated raw water; **Not prechlorinated raw water

Examination of these results lets us make the two following remarks: When chlorine neutralization by sodium bisulfate was carried out upstream of the microfilters, the concentration of the total organic carbon (TOC) in water increased after passage in the microfilters, because of increased biological activity in the microfilter itself. When chlorine neutralization by sodium bisulfate was carried out downstream of the the microfilters, the concentration in TOC fell after passage in the microfilters. This indicates the efficiency of the microfilters in stopping suspended matter in general and organic matter in particular, that is present in the pre-treated water. 4.3. Optimization of the conversion ratio In the second stage of the operations period, the researchers noted the presence of salt crystals. Analysis of the operating condition of the plant revealed in fact that changes of rates of raw water were operating. Indeed during the startup of the plant, researchers increased the conversion ratio by decreasing the rate of raw water, this variation was about 26%, while keeping the membrane production flow at the level of the first stage constant. The raw water supplying the second stage then had an abnormally high salt concentration relative to design conditions, while the antiscalant amounts were kept constant. To remedy

this situation, dose of antiscalant and conversion ratio were adjusted. 4.4. Cleaning of membranes After the identification of the origin of the dysfunction, it was appropriate to establish a cleaning protocol of the membranes, to remove the biofilm and to inhibit the bacteriological activity upstream the membranes. The membrane cleaning protocol consisted of washing the membranes with several chemical solutions: Citric acid. Two percent recirculation during 50 min with velocity of 18 m3/h under 3.7 bar pressure assumed to remove mineral clogging in general. Na EDTA (0.1%) recirculation to dissolve calcium and magnesium salts. NaOH (2%) recirculation to remove the biofilm. Formol (0.5%) recirculation during 50 min assumed to disinfect the membranes surface. In spite of the pre-treatment modification and the chemical cleaning, the pressure drop evolution remained above normal values, and tended to increase. Fig. 5 gives the pressure drop evolution measured for each stage. These pressure drops remained constant in the first stage around 2.75 and 1.5 bar in the second stage for line 1, and 2.6 bar on the first stage and

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Charge loss (bar)

215

2.5 2 1.5 1 0.5 0

1st stage

2nd stage

00H00 12H00 00H00 12H00 00H00 12H00 00H00 12H00 00H00 12H00 12/21/2003 12/22/2003 12/23/2003 Date 12/24/2003 12/25/2003

Fig. 5a. Line 1: pressure drop evolution profile.

3.5

1st stage
3

Charge loss (bar)

2.5 2 1.5 1 0.5 0

08h00 12h00 21h00 02h00 08h00 01h00 06h00 12h00 18h00 00h00 06h00 20h00 02h00 20/12 24/12 25/12

2nd stage

Dates
Fig. 5b. Line 2: pressure drop evolution profile.

1.5 bar on the second stage, for line 2. It appears that the chemical cleaning did not remove the biofouling problem, however it inhibited the bacterial proliferation in contact with membranes. We can simply conclude that the chemical cleaning protocol must be reviewed in terms of kind of reagent, amount, and application condition.

5. Conclusion Even if the undertaken actions did not permit operators to re-establish the start-up pressure drop values in each level of the plant, it allowed focusing on the role of the SBS injection point choice. Then it is important to retain in particular:

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The choice of SBS injection point, meant to

neutralize the residual chlorine, is very important for inhibition of the biofouling appearance. In Tan Tan demineralization plant the SBS neutralization upstream the microfilters generated a high biological activity in these filters which played a bioreactor role. The direct consequence was then membranes biofouling. The chemical cleaning applied did not allow removing the biofouling, the formal is not the appropriate reagent to reach this target. The use of the residual chlorine, after having changed the SBS injection point, gave immediate and efficient results. The chemical cleaning protocol to be optimized have probably to use the sodium hypochlorite or an equivalent reagent to re-establish the start-up working

conditions in Tan Tan reverse osmosis demineralization plant.

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