A COMBINATION OF COGENERATION, EVAPORATION AND MEMBRANE TECHNIQUE FOR LANDFILL LEACHATE TREATMENT

E. GIUST, D. VISINTIN AND C. DEL PICCOLO LED ITALIA Srl - Via Nuova di Corva 86/d, 33170 Pordenone, Italy

SUMMARY: The paper presents a solution realised to solve the problem of treatment of landfill leachate in a site in the north of Paris where two landfills are present: an old closed one and a new one still in operation. Two different types of treatment have been chosen to adapt the solution to the specific characteristics of the two different leachates: Reverse osmosis for the old stable leachate and double stage evaporation coupled with the LFG engines to improve the energetic efficiency of motors on MSW landfill, for the new changing leachate. The paper will describe the dimensioning data, the performances of the plant and the results obtained after one year operation of one installation chosen among about 10 other working plants. An economical evaluation of the Operative costs will be reported too. 1. INTRODUCTION Landfill leachate treatment is an actual point of interest for many landfills managers mainly due to the regulations that are changing in several countries and that impose more restrictions. Traditionally there are several types of techniques applied to landfill leachate treatment: Evaporation Membranes techniques; Biological treatment Chemical-physical treatment. The right choice among these technologies relies on several aspects such as: Quality and analytical characteristics of the leachate; Expected quality of the treated stream; Quantity to treat; Availability of some energy sources. It is recognized (Tzahi Y. Cath et al., 2006) that evaporation and membranes processes are the most suitable one to remove TDS from a wastewater stream and that membranes are frequently used as pre-concentration to other steps. The present paper describes the technological choice that has been performed and consequently realised in an operative treatment plant built in a landfill in the North of Paris in operation since about 30 years.

Proceedings Sardinia 2007, Eleventh International Waste Management and Landfill Symposium S. Margherita di Pula, Cagliari, Italy; 1 - 5 October 2007 2007 by CISA, Environmental Sanitary Engineering Centre, Italy

Sardinia 2007, Eleventh International Waste Management and Landfill Symposium

2. SITE DESCRIPTION The landfill receives about 100000 ton/year of wastes, about 60% of which are municipal waste, 38% industrial waste and 2% of waste from demolition activities. Two basins of about 4500 m3 are used for the leachate collection (from both sites). 2.2 km of canalisation collect the about 800 Nm3/h of biogas that is produced with a methane content of about 45%. In 2001 a leachate treatment plant with an oxidation and a filtration through activated carbon was installed, but after some years it wasnt able no more to produce an effluent respecting the discharge limits. Actually about 10000 ton/year of new leachate as well as 10000 ton/year of old leachate need to be treated on site. After analyses and laboratory tests, two different solutions for the two different leachates have been identified: Reverse osmosis for the old leachate from the closed landfill since this leachate is quite dilute and stable; Evaporation technology for the new leachate from the active landfill since this leachate is developing and its characteristics are changing thus requiring a flexible type of treatment as evaporation is. In Table 1, the characteristics of the leachate of the old site are reported. The average values have been obtained considering weighted values of the last years. Table 1 - Raw leachate composition: old site pH Suspended solids Chemical Oxygen Demand (COD) Biological Oxygen Demand (BOD) BOD/COD Conductivity Chlorides NH4+ Total Heavy metals Minimum 8,0 10 251 10 3% 3796 530 102 2,9 Maximum 8,4 510 629 38 6% 6795 5500 234 5,1 Average 8,1 16 314 13 4% 4295 960 118 3,6

mg/l mg/l O2 mg/l O2 S/cm mg/l Cl mg/l N mg/l

In Table 2, the characteristics of the leachate of the new site are reported. The average values have been obtained considering weighted values of the last 3 years, since the beginning of the leachate production. Table 2 - Raw leachate composition: new site pH Suspended solids Chemical Oxygen Demand (COD) Biological Oxygen Demand (BOD) BOD/COD Conductivity Chlorides NH4+ Total Heavy metals Minimum 6,2 53 290 198 68% 1860 284 31 0,2 Maximum 7,6 150 1770 1190 67% 5505 5300 185 1,0 Average 7,2 137 920 506 55% 4935 3300 118 0,8

mg/l mg/l O2 mg/l O2 S/cm mg/l Cl mg/l N mg/l

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In Table 2 its quite interesting to notice the ratio BOD/COD that is quite high and compatible with a new produced leachate. The ammonia and chlorides concentrations are also increasing as expected. The two parts of the plant are in reality connected: the RO concentrate is in fact father concentrated by the Evaporation plant to reduce the final volume to dispose at maximum, to solve in this way also one aspect related to Reverse Osmosis technology enhanced by some literature that is the relatively low concentration achievable through RO system (S. Hercule et al, 2003), while the condensate of the evaporation is sent to the RO for final polishing before discharge. On site, the biogas is recovered to feed a cogeneration plant and produce electrical energy that is sold. ON site only one engine of 1 MW was installed. For this reason it was necessary to exploit both the cooling of engines and the exhaust combustion gases in order to obtain the necessary 950 kW (thermal heat) for the evaporation process. The landfill gas valorisation to produce electricity induces a loss of energy due to the engines cooling system and the combustion exhaust gases. In order to take benefit of this energy, two companies, LED ITALIA and GRS VALTECH developed a way of cogeneration through leachate treatment (Hercule et al. (2005)). This process complements the evaporation technology using direct landfill gas, rather implemented on lower LFG production site (E. Cornu et al, 2003).

2. FUNDAMENTALS OF THE CHOSEN TECHNOLOGIES 2.1 Reverse osmosis technique The phenomenon of osmosis occurs when pure water flows from a dilute saline solution through a membrane into a higher concentrated saline solution. The phenomenon of osmosis is illustrated in Figure 2.1. A semi-permeable membrane is placed between two compartments. Semi-permeable means that the membrane is permeable to some species, and not permeable to others, if the membrane is permeable to water, but not to salt. And if this membrane is placed to divide a salty solution in one compartment and pure water in the other compartment, the phenomenon that occurs is that the membrane will allow water to permeate through it to either side and salt cannot pass through the membrane.

Figure 1: Reverse Osmosis concept

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With a high pressure pump, feed water is continuously pumped at high pressure to the membrane system. Within the membrane system, the feed water will be split into a low-saline and/or purified product; called permeate, and a high saline or concentrated brine, called concentrate or reject. A flow regulating valve, called a concentrate valve, controls the percentage of feed water that is going to the concentrate stream and the permeate which will be obtained from the feed. The key terms used in the reverse osmosis / nanofiltration process are defined as follows. Recovery - the percentage of membrane system feed water that emerges from the system as product water or permeate. Membrane system design is based on expected feed water quality and recovery is defined through initial adjustment of valves on the concentrate stream. Recovery is often fixed at the highest level that maximizes permeate flow while preventing precipitation of super-saturated salts within the membrane system. Rejection - the percentage of solute concentration removed from system feed water by the membrane. In reverse osmosis, a high rejection of total dissolved solids (TDS) is important, while in nanofiltration the solutes of interest are specific, e.g. low rejection for hardness and high rejection for organic matter. Passage - the opposite of rejection, passage is the percentage of dissolved constituents (contaminants) in the feed water allowed to pass through the membrane. Permeate - the purified product water produced by a membrane system. The dimensions of the pores of the membranes used for Reverse osmosis are suitable to reject the ions of a salty solution, thus producing a permeate with very low salinity and conductivity.

Figure 2: Flow inside an RO module Flow - Feed flow is the rate of feed water introduced to the membrane element or membrane system, usually measured in gallons per minute (gpm) or cubic meters per hour (m3/h). Concentrate flow is the rate of flow of non-permeated feed water that exits the membrane element or membrane system. This concentrate contains most of the dissolved constituents originally carried into the element or into the system from the feed source. It is usually measured in gallons per minute (gpm) or cubic meters per hour (m3/h). Flux - the rate of permeate transported per unit of membrane area, usually measured in gallons per square foot per day (gfd) or liters per square meter and hour (l/m2h). 2.2 Evaporation technique Evaporation technique is a physical separation of a solvent from a solution through heat supply; in wastewater treatment the solvent is water that is separated from a water-based solution containing pollutants of different nature. There are several techniques that can be used to perform this type of separation that can differ on:

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The type of energy source: electrical energy Steam Hot water The type of circulation: Natural in which the liquid naturally flows inside the heat exchanger with low speed; Forced in which the liquid is pumped inside the heat exchanger by a pump at a certain rate that gives the advantage of higher concentration factors, lower fouling phenomena and consequently lower maintenance. The type of technology: Mechanical vapour recompression: thermodynamically, it is the most efficient technique to evaporate water. This process takes the vapour that has been evaporated from the product, compresses the vapour mechanically and then uses the higher pressure vapour as heating medium to perform the evaporation of the new inlet wastewater. Single stage or multi stage hot water/steam: types of evaporators that use hot water/steam and cold water stream for evaporation/condensation. They can be single effect or multi effect: in case of multi effects evaporators the steam produced from evaporation in one effect is used to provide the heat to evaporate product in a second effect which is maintained at a lower pressure. The multi-effects system lowers energy consumption but increases the complexity of the plant and the setting of the working parameters. Thermocompression: when steam is available at a certain pressures, it will often be possible to use thermo vapour recompression. In this operation, a portion of the steam evaporated from the product is recompressed by a steam jet venturi and returned to the steam chest of the evaporator. Heat pump: In a heat pump evaporator, the energy required for heating and condensing is transferred in a closed circuit by a refrigerant gas, normally Freon. This gas is heated by a compressor and pumped to the primary heat exchanger where heat is transferred to the wastewater. The wastewater is continually circulated from the boiling chamber through the primary heat exchanger and back again. Upon return, flash evaporation takes place due to the boiling chambers lower pressure and temperature relative to the wastewater. In the heat pump circuit, the Freon gas flows through an air cooled radiator and expands. As the gas expands, it cools down and then passes through the tubes of a condenser in the upper part of the boiling chamber. Heat is absorbed from the wastewater vapour causing condensation on the condenser tubes. This condensate is collected and flows to the distillate tank as clean water. The gas returns to the compressor. Evaporation produces two streams: A treated major stream called condensate where all the suspended solids, heavy metals and salinity are completely removed and most part of organics compounds are absent; A concentrate that is a minor part of the inlet that contains all the pollutants. Some definitions that are useful while talking of evaporation are: Yield - ratio between the quantity of condensate produced and the inlet. Concentration factor - parameter related to the yield that indicates how many times the wastewater has been concentrated. For example a yield of 90% means that if 100 litres enter an evaporation system 90 litres are recovered as condensate that can be reused inside the production cycle (in industries) or discharged if the reuse is not possible, and only 10 litres constitute the final residue. In this case the concentration factor is 10. Boiling point rise - colligative property that corresponds to an increase in the boiling temperature related to the presence of solutes in a solution.

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3. PROJECT DESCRIPTION 3.1 Old landfill The treatment of landfill leachate by means of reverse osmosis requires an adequate conditioning of the leachate before entering the RO modules in order to preserve the plant performances. For this reason the plant is designed with: A pH adjustment and a degassing; Multimedia filtration; Chemical conditioning (antiscalant dosing) Cartridge safety microfiltration Multi stage double passage reverse osmosis. 3.1.1 PH adjustment and degassing This step is performed in order to displace both ammonia equilibrium towards its salified form NH4+ that is more soluble in water and better rejected by RO and bicarbonates normally present transforming them in gaseous CO2. For this reason a degassing is necessary. The right pH value has been identified to be around 6: at this value in fact the chemical displacements of the 2 equilibria are realized and at the same time no precipitation of organics occur (Wui Seng Ang et al., 2005). 3.1.2 Multimedia filtration The first filtration step is carried out by a multimedia filtration bed specially suited for the quantitative removing of the suspended solids, with the minimization of the washing procedure; this filtration it is called volume filtration and it is realized with a multilayer (filtration media with different sizes and densities) filtration bed containing quartzite and anthracite. The second filtration step is carried out by a multimedia filtration bed specially suited for the catalysis of the oxidation and the quantitative removal of heavy metals like iron and manganese. The presence of these two heavy metals can affect heavily the fouling process of the membranes and provide also big problems during cleaning procedure. This second filtration step is also a safety filtration step itself due to the strictly degree of filtration obtained by this media. The filtration bed is composed by quartzite and activated pirolusite. 3.1.3 Chemical conditioning An antiscalant chemical is metered in order to limit scaling phenomena in the concentration steps. 3.1.4 Cartridge safety microfiltration The landfill leachate is then entered in the cartridge filtration. The degree of filtration of the cartridge filters is 5 micron, in this way we can remove all the smaller particles that could be formed during chemical conditioning or that are possibly leaked through the multimedia filter. The filters cartridges can be easily substituted, this step is essential for the safety utilization of the reverse osmosis membranes. Special cartridge filters are utilized; they are obtained by the melt blow technology with two effective degree of filtration in series in the same cartridge providing a volume filtration. 3.1.5 Multi stage double passage Reverse osmosis Landfill leachate is now pressurized to the reverse osmosis modules of the first concentration

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passage, where nearly all dissolved salts and organic substances are held back, while pure water is forced through the semi permeable membranes. The plant is completely automatic and it is realized with a multi stage and double passage configuration in order to reach on one side high recovery and on the other an excellent quality of the permeate making it suitable for discharge. The process conditions are strictly controlled by the utilization of field instrumentation controlled by the PLC. The flow rate produced by every membrane array and the inlet and outlet pressure of every membrane array are controlled, in this way the system continuously evaluates the fouling degree of the membranes and automatically can provide the cleaning procedure of the membranes when necessary with suitable and tested chemicals (Tragardh (1989), Madaeni et al (2001), Tran-Ha (2005)) using the CIP (Cleaning in Place) systems installed. The second passage for the permeate polishing is realized with one concentration stage. The RO plant is dimensioned for a capacity of 3 m3/h in order to have enough capacity also for the treatment of the evaporators condensates from the new landfill for polishing before discharge. The quality of the permeate is reported in Table 3 at chp. 4. The RO plant works with a recovery of about 90%, producing about 2.7 m3/h of permeate and 0.3 m3/h of concentrate that is sent to the evaporation plant.

3.2 New landfill The choice of evaporation technology was made to meet the requirements of the discharge criteria as well as to have a very flexible technology able to treat a developing stream and the concentrate produced by the RO system. A second stage of evaporation allows a reduction of the volume of final concentrate. The yearly water balance is about 10000 m3 per year. The designed feeding rate is thus 30 3 m /d. To take benefit of the energetic loss of landfill gas engines, a cogeneration plant was designed. This plant improves the 1000 kW energetic potential of the engines cooling system. Thus, the hot water used to cool the engines circulates in the shell side of a plate exchanger, which re-heat the influent. Part of the heat is recovered also from the fumes of the engines. Each treatment step is detailed in the paragraphs below.

Figure 2. Simplified flow-sheet of the evaporation plant for new leachate treatment

Sardinia 2007, Eleventh International Waste Management and Landfill Symposium

The process line for the treatment of the leachate of the new landfill is: A pH adjustment and a degassing; First evaporation/concentration step: Hot water forced circulation evaporator Second evaporation/superconcentration step: scraped hot water superconcentrator 3.2.1 PH adjustment and degassing This step is performed in order to displace both ammonia equilibrium towards its salified form NH4+ that is more soluble in water to limit its passage in the vapour phase (Berbenni et al, 1997) and bicarbonates normally present transforming them in gaseous CO2. For this reason a degassing is necessary. Working at an acidic pH (5-5.5) lowers also scaling phenomena that can happen with the increase of concentration inside the boiling chamber. 3.2.2 First evaporation/concentration step In Fig. 3 a process scheme of the evaporator EW 40000 FF is reported as reference for the description.

Figure 3. Simplified flow-sheet of the evaporation plant for new leachate treatment

Sardinia 2007, Eleventh International Waste Management and Landfill Symposium

The liquid is sucked inside the boiling chamber of the evaporator EW 400000 FF by the vacuum created inside it (4-5 kPa) by the liquid ring pump coupled with the ejector that works with Venturi principle using air as motor fluid. A circulation pump sends the liquid from the bottom of the boiling chamber inside the shell and tube heat exchanger where it receives the necessary neat from the hot water stream that circulates inside the heat exchanger. Once heated, the liquid returns to the boiling chamber, where as a result of the vacuum, a portion of the liquid immediately boils (flash evaporation). The vapour rises through the demister in order to damp the droplets. Vapour is condensed against the U tubes of the heat exchanger. The steam condensation is then performed by an air cooler mounted on the evaporator. The vacuum system extracts the condensed distillate together with any incondensable gases and sends them to a storage tank. The distillate and the concentrate are discharged through a pump. All operations are controlled by a PLC. The hot water comes from the cogeneration plant, while the cold water for condensation come from the air cooler mounted over the top of the evaporator. The EW 40000 unit works with a yield of about 93% producing about 2.5 tonyday of concentrate that is sent to another concentration step for further concentration and reduction. 3.2.3 Second evaporation/superconcentration step A second step of vacuum evaporation is set up to lower the volume of final residues. The concentrate produced by the first stage of vacuum evaporation feeds a scraped evaporator RW 3000 FF under vacuum for the same reasons explained for the EW 40000 unit (see the process scheme on the figure 4).

Figure 4: Second step of evaporation: scheme of the scraped evaporator

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The lower part of the boiling chamber is made by a heating jacket heat exchanger. The heat is provided by the system used on the first stage of evaporation: a part of hot water, from the engines cooling system, flows into the heating jacket. The concentrate is evaporated through heat diffusion of the exchanger walls. A very efficient scraping Archimedes screw, driven by an electric motor reducer, allows an efficient stirring and the cleaning of the exchanger walls and allows to treat effluents with very high solids content and to produce a semi-solid concentrate. The temperature of evaporation is ranging between 35 and 45 C for a residual pressure of 5 6kPa. The steam produced by the evaporation of concentrate is condensed on the air cooler mounted on the fist evaporator. The condensate is collected together with the one of the EW and treated by the RO. A centrifugal pump coupled to an ejector assures the vacuum in the boiling chamber. The evaporation process is conducted on batch run basis. The operating cycle is fixed by the level control in the boiling chamber. At the end of each cycle, the concentrator is stopped and residues are discharge by rising and bending the chamber. The final concentrate is moved along the boiler chamber by the Archimedes screw. Temperature sensors are used to control the evaporation process and the amount of heat transfer, in association with the flow rate sensor. Thus the global volume of residue is lowered, as a function of dry solids limits into the evaporator. The RW unit works with a yield of about 80-85% producing a final concentrate to dispose of about 0.3 ton/day with a total solid content of approximately 70-75%.

4. RESULTS AND DISCUSSION 4.1 Qualitative and quantitative results The plant was commissioned beginning of 2006: after one year operation no relevant episodes happen both from process point of view and from electromechanical point of view. Due to the interconnection of the 2 plants, the evaporation units and the RO unit, only 2 streams come out as output: the RO permeate for discharge and the RW concentrate for final disposal. In Table 3 the quality of the permeate is reported as well as the limits fir discharge imposed by the authorities. Table 3 Quality of the final permeates and limits for discharge pH Suspended solids Chemical Oxygen Demand (COD) Biological Oxygen Demand (BOD) Conductivity Chlorides NH4+ Permeate 5,5 <2 <30 <5 30 <1,0 <0,5 Limits 5 100 20 15

mg/l mg/l O2 mg/l O2 S/cm mg/l Cl mg/l N

The permeate produced is characterized by a higher quality than the one required for discharge with a reduction of more than 99% for the salinity (conductivity) and of about 97% for the organic compounds (COD).

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Some considerations for the concentration factors and the volume reduction: considering the combination of the two leachates that give an amount of approximately 60-65 ton/day of wastewater to treat, the final volume to dispose consists of just about 300 kg of semi-solid concentrate, thus achieving a total recovery of more than 99% with a huge reduction of disposal costs. 4.2 Operative costs In the following table the operative costs encountered during the year of functioning of the plant are reported expressed as per ton of treated leachate: The use of a free source of energy, the thermal heat available on site and recovered from the energy production plant, allows to lower the global energy consumption for the evaporation process with a decrease of operating costs. The recovery of thermal heat from the energy production engines otherwise lost increases the global efficiency of the energy production plant: this is also a point very much appreciated by local authorities that give value to this increase in efficiency with a corresponding increase in the price of selling of electricity taking higher income to the landfill management. Table 4 Operative costs U.M. Electrical energy /kWh Energy consumption kWh/m3 Cost for energy /m3 Chemicals (antifoam, acid etc.)+ /m3 counsumables Maintenance /m3 Cost for Conc. Disposal /ton Quantity of conc. To dispose Ton/day Cost for disposal per ton of leachate /ton Total /ton Value 0,06 35 Opex

2,1 3,5 1,3 300 0,3 1,5 8,4

5. CONCLUSIONS The experience in this landfill in the north of Paris shows that coupling evaporation techniques with membranes processes gives very good results in leachate treatment: producing a treated stream of excellent quality and reducing the final volume to dispose as maximum, up to a semisolid product. The relevant results come from the integration of the peculiarities and best qualities of the two technologies that more and more can be proposed as a combined solution. The installation demonstrates also the effectiveness of combination of cogeneration and evaporation: the recovery of thermal power from cogeneration plant allows to sustain evaporation technology that can solve the problem of landfill leachate treatment at very low running costs thanks to the free energy source that is used as feed. This combination increases also the global efficiency and this more effective exploitation of resources correspond to an increase of income that comes from the higher price for the selling of energy that authorities recognize for the successful operation.

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REFERENCES Berbenni P., Pollice, A., Fedrigoni, F. & Ceresi, G. (1997) : The vacuum evaporation process for landfill leachate treatment. Sardinia 1997, Sixth International landfill Symposium, CISA publisher, Cagliari. Cornu E., Ballot J., Bentouns N., Pernot H., and Hercule S. (2003) : Leachate treatment using landfill biogas. Proceedings Sardinia 2003, Ninth International landfill Symposium, CISA publisher, Cagliari Hercule S., Taramini V., Samat P., Giust E., Biquillon R. (2005) : Cogeneration and evaporation: an example of leachate treatment. Proceedings Sardinia 2005, Tenth International landfill Symposium, CISA publisher, Cagliari. Hercule S., Cornu E., Ballot J., Coquant C., Dumesnil C. and Lebourhis D. (2003) : Review of in-situ leachate treatment plant : 3 case studies in France. Proceedings Sardinia 2003, Ninth International landfill Symposium, CISA publisher, Cagliari. Madaeni, S.S., Mohammadi, T., Moghadam, M.K., 2001. Chemical cleaning of reverse osmosis membrane. Desalination 134, 7782. Tragardh, G., 1989. Membrane cleaning. Desalination 71, 325335. Tran-Ha, M.H., Santos, V., Wiley, D.E., 2005. The effect of multivalent cations on membraneprotein interactions during cleaning with CTAB. J. Membr. Sci. 251, 179188. Tzahi Y. Cath, Amy E. Childress, Menachem Elimelech (2005): Osmosis: Principle, applications and recent developments, Journal of Membrane Science, Elsevier. Wui Seng Ang, Sangyoup Lee, Manechem ELimelech (2005): Chemical and physical aspects of cleaning of organic- fouled reverse osmosis membranes, Journal of Membrane Science, Elsevier.