Documentation Technical Project LTP Olt

THE REASONS TO CHOOSE MBR+NF TECHNOLOGY

1. PROBLEMS TO REACH THE TENDER REQUIREMENTS WITH SBR TECHNIQUE

Setting too low feed concentrations In the bidding too low COD and BOD concentration is determined for the leachate. It is believed a COD concentration in the feed of 2.650 mg COD/ l. We believe that this concentration level for far too low. Based on our experience much higher concentrations have to be assumed considering the waste characteristics and climatic conditions. In the realized by Wehrle Umwelt leachate treatment plants concentrations below 2.650 mg COD /l are only found in old landfills (where separate collection of bio waste, possibly with mechanical-biological treatment of residual waste has been applied). The leachate concentrations known to us in the dumpsites in Eastern Europe are between 5.000 mg/ l and 15.000 mg/l. We therefore recommend a significantly higher concentration for the design. Since the higher COD concentrations lead to higher sludge production, the required minimum sludge age for nitrification results either a significantly enlarged bioreactor volume or modified solids retention by means of ultrafiltration. As an ultrafiltration additionally increases the process stability and lower outlet values are achieved, we have chosen this option. To comply with the requirements a post treatment by means of a downstream membrane system (reverse osmosis or nanofiltration) should be foreseen. The biomass retention by ultrafiltration offers several other advantages. The solids and BOD free flow after ultrafiltration provides optimal benefits for further treatment in the downstream membrane system. The latter gives the opportunity to use membrane elements with a smaller spacer. With the fully liberated from the BOD biology the bio-fouling problem in the membrane post stage is significantly mitigated. This reduces cleaning intervals and leads to a significantly longer membrane lifespan. The arguments for an MBR technology over a SBR technology are again summarized below in chapter 6.

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2. ADVANTAGES MBR VS. SBR

2.1 Higher Biomass Concentration

The biomass concentration in an MBR is with 15 kg/m much higher than in an SBR System (3-5 kg /m). Therefore the reactor volume of an MBR is far smaller than that of an SBR, usually only 15 20 % of the SBR Volume. 2.2 Better COD removal

The Ultrafiltration, which is part of an MBR process, achieves a complete biomass (= 0 solids or biomass in UF permeate) retention whereas the biomass retention of an SBR is fairly poor. This means that the solid-free effluent of an MBR has a better COD, because a) The solids themselves are organic particles and contribute to the COD. b) The complete retention of all biomass in the MBR Systems results in a high concentration of specialists which achieve a better COD removal rate. c) A thin layer in the Ultrafiltration acts itself as screen and retains additionally a part of the COD The COD in the effluent of an MBR is 30 to 60 % lower than the effluent from an SBR! 2.3 Higher process stability

There is yet another aspect to the biomass retention of an SBR: In case feed concentrations to the SBR vary greatly, or in case the feed contains toxic substances or in case the composition of the feed quality varies considerably, the quality of the biomass in the SBR changes. The settling behavior worsens and thus the SBR is prone to lose substantial amounts of biomass (= solids) with the treated effluent. This means a higher COD in the treated effluent (more solids = higher COD). If this lasts for longer, SBR loses too much of its active biomass and the complete biological process becomes seriously disturbed of not to a stand-still. In that case only a complete refill of the bioreactor with new sludge can help. Of all biological processes that there are on the market, the MBR is the most stable, most robust process due to the fact that the biomass is completely retained and the adaptation possible of the biomass can be achieved. 2.4 Shorter start up time of the system

Because of the Ultrafiltration and its positive effect on the biomass adaptation, the start-up phase of an MBR is far shorter than that of other biological processes. 2.5 Higher stability against variation of the influent concentration

Again: Because of the Ultrafiltration and its positive effect on the biomass adaptation, an MBR can handle strong variations in feed flow, feed load and feed composition better than any other biological process. 2.6 More flexibility against high salt concentrations

An MBR can handle high salt concentrations of up to 25 g/l stably and without negative sideeffects!
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2.7

No pH variation in the system, no chemical dosing for pH stabilization

In case a denitrification is required, an MBR works with a pre-denitrification = a separate denitrification tank, which is installed in front of the nitrification and which works simultaneously to the nitrification. This results in an improved pH stability compared to an SBR. In an SBR, pH fluctuations are considerable because the stabilizing process of the denitrification is separated in time from the nitrification process the process which triggers the pH changes. Usually, these pH changes need to leveled by dosing caustic in the SBR process. Indeed can the pH ups and downs of an SBR be alleviated by shortening the intervals / phase durations. Yet this finds its limitations when COD and/or N loads are high and may lead to the inhibition of the nitrification. 2.8 Lower NH4-N concentration in the effluent

An MBR can well & stably achieve NH4-N concentrations of < 5 mg/l in an SBR, higher NH4N concentrations in the treated effluent must be accepted due to the inhering process conditions. Depending on the pH and the temperature in the SBR reactor, nitrogen is available in form of NH3-3 a molecule which is toxic to biomass and often inhibits the nitrification process. An SBR also is sensitive to changes in the nitrogen concentration in its feed. The duration of the single intervals (phases) then determine the maximum N-concentration that may occur in the reactor the shorter the interval, the higher the N-peaks in the reactor, the less nitrification. In order to maximize the process stability, the duration of the intervals must be maximized. The design parameter for the interval length is the maximum NH4-N concentration in the feed. Yet in reality, the maximization of the nitrification phase is limited because of the limited reactor volume and the time that is required for the sludge settling. Therefore SBRs are usually designed for an average N-concentration in the feed. And because of the natural laggardness of the system and because the duration of the intervals cannot be changed spontaneously, an SBR can only poorly cope with variations of nitrogen in the feed. 2.9 More possibilities in choosing the right post treatment

Since an MBR can reliably deliver an effluent with very low NH4-N concentration, a subsequent process for the removal of remaining NH4-Nis not required. 2.10 Higher efficiency in terms of the denitrification process An SBR is a completely mixed reactor, therefore high BOD concentrations are neither to be found nor are they desired. But unfortunately, the reduction of NO2-N or NO3-N is the faster, the higher the BOD concentration. In the separate denitrifcation reactor of an MBR, the current inside the reactor can be directed by inducing a plug flow. The plug flow creates a gradient in the BOD/COD concentration in the denification reactor. In this way, the COD/BOD of the feed can be used very effectively for the denitrification process and this is why in an MBR a higher denitrification velocity and lower carbon source can be achieved compared to an SBR. 2.11 Reduced installed power capacity under the same effluent criterias Up to the intermediate aeration the installed blower power in an SBR System is much higher than the installed capacity in a Membrane Bioreactor. Because the different processes of an
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SBR are taking place one after the other, the nitrification has to take place within a short time span = the required air must be inserted in a short time = the blowers must be bigger to provide sufficient air in a short time span. 2.12 Cost reduction in the post treatment In case further treatment steps are required by a client (e.g. if salts reduction is required or a particularly low COD must be met with), an MBR is at an advantage: because of the maximal COD removal and the complete solids retention of an MBR, the installations required for any subsequent treatment step become simpler and more effective = the subsequent treatment steps become cheaper + smaller! For example: In case of a post-treatment with membrane Technology (RO or NF) a sand filter for example is not necessary. Another advantage is the possibility to work with standard spiral wounded membranes. These kinds of membranes are much lower in the CAPEX and in replacement costs. The price for a standardized spiral wounded membrane is around 30 50 per m2. The price for a comparable plate membrane is around 150 per each m2. In a post RO System the membrane lifetime expectations is around 1.5 to 2 years, so this argument is highly relevant for the operational cost of the whole system. 2.13 Lower wet sludge volume Up to the lower sludge load in the MBR and up to the higher MLSS the wet sludge Volume is significant lower than in an SBR System. Any biological process produces surplus sludge = microbes multiply and grow in the reactor, the MLSS increases over time. Therefore sludge must be removed from any reactor from time to time. Because the MLSS concentration in an MBR is far higher than in an SBR to begin with and because the surplus sludge can be withdrawn from the pipe with the thickened sludge coming back from the Ultrafiltration, the volume of surplus sludge of an MBR is far less than that from an SBR system. 2.14 Higher Temperature in winter times

Up to the smaller volume and a higher Biomass activity the MBR Reactor has a higher temperature in winter times. This makes the nitrification more process stabile also in long frozen phases. The influent effluent heat exchanger gives the heat from the effluent to the influent that helps to increase the Temperature in the Bioreactor also. MBR Plants under operation in North China, South Germany, Austria and Switzerland demonstrate that the MBR is able to reduce the Ammonia less than 10 mg/l also during winter times. Against this there are many SBR Reactors with temperature problems during winter time so some leachate plants need heat from the gas motors to increase the temperature.

3. REASONS FOR POST TREATMENT WITH NANOFILTARION

In the tender a too high removal rate of the SBR reactor is expected. There are outlet requirements defined in the tender that a classic SBR system, even with very conservative design cannot keep. The following table lists the parameters COD, BOD, and ammonia nitrogen. The expected outlet concentrations of the SBR reactor exceed the demanded acc. to the tender values significantly. Also, the membrane bioreactor will not reach the requirements in respect to the parameter COD. Fulfillment of the requirements can only be reached with a further downstream membrane step. A single-stage nanofiltration is to be employed. The nanofiltration ensures that the requirements for the COD can be also achieved. In principle, a
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reverse osmosis would have been possible as well; the reasons for choosing a nanofiltration are explained in Chapter 8. Parameter Leachate Inlet From To Effluent values Discharge SBR limits 0-35 6,5-8,5 60 25 125 3 2 0,1 0,5 1 600 0,3 20 0,5 0,2 0,2 1 0,1 0,1 0,5 0,5 1 0,2 <50 <750 <50 MBR MBR+NF

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23

Temperature pH Suspended matter BOD5 COD NH4+ PO4-P Cyanides Sulphides Sulfites Sulphate Volatile phenols Extractable substances Tensides Plumb Cadmium Chromium total Chromium 6+ Copper Nickel Zinc Manganese total Free chlorine

mg/l

6,5 200

8,5 500 1,750 2,650 800 10 2 5 50 2,500 200 100 50 1 1 1 1 1 1 1 5 3

mg/l 500 mg/l 2,000 mg/l 200 mg/l 0 mg/l 0 mg/l 0 mg/l 0 mg/l 200 mg/l 0 mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l 0 0 0 0 0 0 0 0 0 0 0

<25 <500 <3

<25 <125 <3

4. REVERSE OSMOSIS VS. NANOFILTRATION

4.1 Raw wastewater treatment, simple biological pre-treatment or efficient biological pre-treatment Which influence does the dimensioning of the biological treatment have on the membrane plant operation?

WEHRLE generally sees the membrane technology (osmosis and nanofiltration) as posttreatment to an efficient biology. An efficient biology reduces the BOD and the NH4 below 5 mg/l. The biomass separation is carried out by using a membrane. Therefore, no filtrated matter can pass into the membrane plant. This means that modules with a very high packing density can be used. Consequently, the investment and operating costs for the membrane plant can be reduced significantly. Competitors who offer their own membranes and modules reject the efficient membrane biology as pre-treatment since this would make the use of their usually overpriced own
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membranes and modules unnecessary. This is why many competitors prefer membrane plants without biological pre-treatment or with a very simple biological pre-treatment. A simple biological pre-treatment reduces the BOD but does not achieve stable nitrogen elimination (NH4-N mostly no removal or NH4-N concentrations < 100 mg/l). The biomass separation is usually carried out by using sedimentation. High concentrations of solids can very often be found in the outlet of those plants. Moreover, in certain plants, the nitrogen is not eliminated biologically but stripped by the exhaust air of the biology. Besides, high NO2N concentrations can often be found in the outlet of the biology. Yet it must be considered that the nitrite nitrogen (NO2-N) is registered as part of the COD. 4.2 Retention of monovalent and bivalent ions

Osmosis membranes retain matters with a particle size below 0.0001 m or with a molecular weight below 100 mg/mole. By using osmosis membranes, a complete retention of the inorganic matter is achieved. Nanofiltration membranes retain matters with a particle size from 0.0001 to 0.01 m or a molecular weight below approximately 400 mg/mole. By using nanofiltration membranes, the inorganic matters are partly retained. Monovalent ions, such as chloride, are only retained to a very small extent. The retention of bivalent ions, such as sulphate, is significantly higher. 4.3 Retention of organic matters (BOD)

Using membrane technology in wastewater treatment, the membrane Cut-off is determined by the molecular weight of the matter which is to be separated. However, in wastewater treatment, no particular single matter is examined. Instead, the sum parameters BOD and COD are used for those applications. BOD-causing matter is usually low-molecular and can consequently be decomposed biologically very easily. The low-molecular ions are not properly retained by the nanofiltration, which is why nanofiltration to retain BOD-causing matter is not a suitable solution. The BOD-causing matter is better retained by reverse osmosis. However, it has to be considered that the BOD compounds have a negative influence on the operating performance of the plant. Those matter causes high biofouling and makes a frequent chemical cleaning of the membranes necessary. A frequent chemical membrane cleaning wears out the membranes and reduces the membrane lifetime. As a consequence, even well-known osmosis suppliers recommend a biological step for the treatment of very highly loaded organic wastewater, such as wastewater from mechanical-biological waste plants or highly loaded leachate. 4.4 Retention of organic matters (COD)

Since the parameter COD also contains BOD-causing matter, the COD-retention by nanofiltration is a function of the COD/BOD ratio in the inlet. If there is a biological pretreatment, the ratio is very high as the biology has already decomposed the low-molecular BOD-causing matter. In this case, the COD retention by nanofiltration is approximately 85 to 95 %. If the COD/BOD ratio of the wastewater treated by the nanofiltration is very low, the retention of the nanofiltration is only 40 to 60 %. Therefore, a nanofiltration can only be recommended as post-treatment to a very efficient biological wastewater treatment. The situation is very similar for an osmosis membrane. If the COD/BOD ratio is high, 95 to 98 % are retained. If the COD/BOD ratio is lower, 80 to 95 % are retained. Due to the
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better retention of low-molecular matters the reverse osmosis can also be used without biological pre-treatment for low-loaded or medium-loaded wastewater. 4.5 Retention of ammonia-nitrogen (NH4-N)

Ammonia nitrogen (NH4-N) and ammonia (NH3-N) are in dissociation equilibrium. The nanofiltration neither retains NH4-N nor NH3-N. An osmosis can retain NH4-N but NH3-N only to a very small extent. In order to ensure retention, a pH reduction and, consequently, an adjustment of the equilibrium towards NH4-N are necessary. If the pH values are between 6.0 and 6.5, retention of NH4-N of > 90 % is possible. 4.6 Retention of nitrogen oxides (NO2-N and NO3-N)

A nanofiltration is not able to retain the NO2-N molecule. The retention of NO3-N is between 30 and 60 %. An osmosis membrane is able to retain both compounds very well. 4.7 pH adjustment (acid dosing) in nanofiltration and reverse osmosis

In both processes, the pH should be reduced in order to avoid inorganic precipitation on the membrane. For the nanofiltration, depending on the concentration of the inorganic matter, the adjusted pH value is between 6.7 and 7.0. For an osmosis membrane, the pH value is usually adjusted at a slightly lower level (pH between 6.5 and 6.8). If there are high ammonia nitrogen concentrations in the wastewater, the reverse osmosis has to consist of several steps (two-step or three-step) or the pH has to be further adjusted (pH between 6.2 and 6.5). It has to be considered that the specific acid consumption is determined by the buffer capacity in the wastewater. For a lot of wastewaters, the high ammonia concentration is crucial for the buffer capacity of the system. If the ammonia nitrogen is not decomposed in a biological pre-treatment, a significantly higher acid consumption to adjust the pH values mentioned above is necessary. Osmosis plants without nitrification as pre-treatment and with disposal of the concentrate back to the landfill body are to be given special attention. By concentrating the ammonia in the circuit landfill membrane plant and back, the necessary acid dosing and, consequently, the increase of the salinity of the landfill body is becoming higher and higher. 4.8 Yield factor of nanofiltration and reverse osmosis

Depending on the characteristics of the wastewater, the yield of the nanofiltration is between 85 and 95 %. The yield of an osmosis plant depends on the plant pressure and on the concentration of the inorganic matter. For the treatment of saline wastewaters, such as leachate, the yield factor of an osmosis plant is between 55 and 70 %. A yield factor of 80 % can only be achieved for very low-loaded leachate. 4.9 Membrane cleaning

Since the nanofiltration membranes in wastewater treatment can only be used after an efficient biological pre-treatment, the NF membrane surface is significantly less polluted. A chemical cleaning is done every 2 to 6 weeks. An osmosis plant for raw leachate has to be cleaned once a week. If there is an efficient biological pre-treatment, the cleaning intervals can be up to 3 weeks.
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4.10 Pressure in nanofiltration and reverse osmosis Due to the low salt concentrations in the concentrate, the pressure in the nanofiltration plants is significantly lower than in osmosis plants. The pressure for a nanofiltration of leachate is between 12 and 25 bar. Depending on the membranes and the plant configuration, the pressure of the osmosis technology used for leachate treatment is up to 50 bars/ 75 bars /90 bars /120 bars. 4.11 Energy consumption in nanofiltration and reverse osmosis Due to the lower pressure, the energy consumption of the nanofiltration is at 2 to 3.5 kWh/m3 inlet. For osmosis plants, depending on the number of steps and on the plant pressure, the energy consumption is at 6 to 15 kWh/m3 inlet. 4.12 Membrane lifetime and membrane replacement costs Due to the less frequent chemical cleaning, the operating lifetime of nanofiltration membranes is between 2 and 4 years. For osmosis membranes without biological pretreatment, the operating lifetime is between 0.5 and 1.5 years. The membrane operating lifetime for osmosis plants with efficient biological pre-treatment is between 1.5 and 2.5 years. 4.13 Colour retention with nanofiltration and reverse osmosis The colour of the treated wastewater is very important for certain applications of industrial wastewater treatment. By using a process combination of membrane bioreactor with nanofiltration post-treatment, complete colour retention is achieved. The colour of the nanofiltration permeate is similar to the colour of reverse osmosis permeate. 4.14 Disposal of concentrate from nanofiltration and reverse osmosis plants back to the landfill Should a disposal of concentrate resulting from osmosis plants back to the landfill body be allowed, it has to be considered how the wastewater constituents should be removed from the landfill body circuit and for which of them a further increase in concentration can be expected during the operation of the plant. If these aspects are not taken into consideration, the concentrate disposal can have a negative influence on the operation of the membrane plant which might even have to be turned down after several years due to too high costs. The following substance groups should be considered: Biodegradable carbon (BOD and partly COD) Non-biodegradable carbon Nitrogen compounds Chlorides Sulphates Carbonates

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The biodegradable compounds are well reduced biologically in the anaerobic bioreactor, i.e. the landfill, on a long-term basis. There is no increase in concentration of those. The landfill as anaerobic bioreactor, however, cannot reduce nitrogen. Without nitrification, stripping or another technical reduction, the concentrations will rapidly increase and, consequently, have a negative influence on the operating costs. Sulphates and carbonates as bivalent compounds will rapidly be reduced in the landfill body since it has to be expected that the leachate contains sufficient counter ions. The chlorides are a very problematic issue since they are difficult to reduce in the landfill body. This is indicated by the very rapid increase in conductivities and the chloride concentrations in the circuit landfill membrane plant and back. This increase could have the following negative influences on the operation of the membrane plant: Yield reduction Increase in acid consumption Shorter membrane cleaning intervals and membrane operating time

With a process combination MBR with nanofiltration as post-treatment, the following substance groups are removed from the circuit: Biodegradable carbon (BOD and partly COD) (in the membrane biology) Non-biodegradable carbon (if necessary flocculation and precipitation or, respectively, activated carbon) Nitrogen compounds (in the membrane bioreactor) Chlorides (discharge via the permeate) Sulphates (discharge via the permeate/precipitations in the landfill body) Carbonates (discharge via the permeate/precipitations in the landfill body)

A process combination of MBR with nanofiltration post-treatment and, if necessary, a physical-chemical concentrate treatment enables an inclusion to the landfill body without having to fear negative influences. 4.15 Treatment of concentrate from nanofiltration and reverse osmosis plants Concentrates from nanofiltration plants with biological pre-treatment are loaded with persistent organic (hard COD) and inorganic matter. Organically bounded- and ammonia nitrogen only exist in low concentrations since they have been removed to a large extent in the biological pre-treatment. In order to treat the COD from the concentrates of NF plants, different process technologies can be used. In the mid-1990s, concentrates were for the first time treated by using chemical oxidation and/or activated carbon in Germany. At the moment, three plants are being operated with activated carbon treatment in Germany. The activated carbon has proved itself because of its simple operation which is less susceptible to malfunctioning. Due to the high COD concentrations, high loading on the activated carbon is achieved. Since 2005, several plants with flocculation and precipitation steps for the treatment of concentrate are being operated in Asia. The reduction of the COD in the NF concentrate does not achieve the concentration levels of an activated carbon plant. However, 50 to 60 % of the non-easily degradable COD compounds can be reduced. The concentrates treated by using activated carbon can be completely led back into the biology due to the high COD elimination degree. Depending on the COD removal, the concentrates treated by using flocculation and precipitation can be partly led back into the biology. If the
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reduction of the hard COD is incomplete, either a powdered carbon dosing has to be carried out or a rest of the concentrates has to be disposed back to the landfill body. Due to the difference in pH value between the pH value of the concentrate (6.0 to 7.0) and the pH value in the landfill body (7.5 to 8.0), the COD compounds are fixed by precipitation of the bivalent sulphate ions in the landfill body. Apart from the described possibilities of concentrate treatment, the nanofiltration concentrates can be further concentrated to a minimal volume by osmosis plants with higher pressure levels. In leachate treatment, the concentrates from osmosis plants have the following characteristic: The inorganic matter is concentrated up to the limits of their solubility product. Due to the high salt concentrations and the precipitation issue, physical-chemical processes to reduce the organic compounds in osmosis concentrates cannot be used. Another possibility to further reduce the concentrates is the thermal treatment by evaporation. This technology is used when the disposal of the concentrates back to the landfill body is not approved. Due to the high operating costs and the very problematic operation, only few evaporation plants to reduce the concentrate quantities are being operated in Europe. Evaporation plants do not achieve a stable discharge, either. The highly concentrated, liquid evaporation rest has to be further disposed of.

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