Desalination 147 (2002) 510

Design and construction of a modular pilot plant for the treatment of oil-containing wastewaters
Jos Manuel Benito*, Guillermo Ros, Enrique Ortea, Eva Fernndez, Angel Cambiella, Carmen Pazos, Jos Coca
Department of Chemical and Environmental Engineering, University of Oviedo, C/ Julin Clavera, 8, 33006 Oviedo, Spain Tel. +34 (98) 5103441; Fax +34 (98) 5103434; emails: jmbm@sauron.quimica.uniovi.es; grr@sauron.quimica.uniovi.es; eof@sauron.quimica.uniovi.es; efp@sauron.quimica.uniovi.es; cheli@sauron.quimica.uniovi.es; cpm@sauron.quimica.uniovi.es; jcp@sauron.quimica.uniovi.es

Received 5 February 2002; accepted 12 March 2002

Abstract A modular pilot size plant involving coagulation/flocculation, centrifugation, ultrafiltration and sorption processes has been designed and constructed. The pilot plant can be used for the treatment of different water-based coolants and oily wastewaters, generated in metalworking processes and steel cold rolling operations. Different treatments are considered depending on the nature of the oily waste emulsion. The main advantage of the plant is its versatility, allowing the combination of several of the aforementioned treatments. It is a feasible waste management alternative with potential savings as a result of a better control of the elimination of oily wastes and water reuse, with the result of environmental and economic benefits. Keywords: Modular pilot plant; Oily wastewater; Ultrafiltration; Centrifugation; Coagulation; Flocculation; Sorption

1. Introduction Oil-in-water emulsions are found in several industrial operations involving two immiscible fluids. Some of them are desirable (e.g. as final products in the cosmetics and food industry), but
*Corresponding author.

in some cases they are undesirable, as in liquidliquid extraction operations, removal of rubber from latex, cleaning bilge water from ships, cold rolling mill effluents, etc. Water-based lubricants and cutting oils have replaced some petroleum-based products in the metalworking industry, especially in steel cold

Presented at the International Congress on Membranes and Membrane Processes (ICOM), Toulouse, France, July 712, 2002. 0011-9164/02/$ See front matter 2002 Elsevier Science B.V. All rights reserved

J.M. Benito et al. / Desalination 147 (2002) 510

rolling operations, as a result of their higher performance. They consists of oil-in-water emulsions, containing mainly emulsified oil and surfactants [1] which allow emulsion formation and stabilization when mixed with water. These emulsified fluids act as lubricants and coolants in metalworking operations, in order to reduce friction between the metal and mechanical equipment, and to avoid metallic piece oxidation and contact welding of metal parts. After being used the fluids become less effective because of their thermal degradation and contamination by substances in suspension, and therefore they must be replaced periodically, generating a waste stream called spent cutting-oil. Spent cutting-oil emulsions are one of the largest volumes of oily wastewaters in metalworking industries. They must be treated before its disposal, due to their detrimental effects on aquatic life and their interference with conventional wastewater treatment processes. Several physicochemical methods for the treatment of spent cutting-oils, such as settling [2], chemical treatment [3], dissolved air flotation [4], centrifugation [5], sorption processes [6] and membrane techniques, mainly microfiltration, ultrafiltration and reverse osmosis [79], have been investigated. The currently available methods (chemical,
- REGENERATION - COMBUSTION - DESTRUCTION

mechanical and electrical) for the separation of emulsified oils has been reviewed recently [10]. Spent cutting-oils may contain inorganic, organic and biological contaminants, present a difficult waste treatment problem because of their diverse composition and concentration, which vary from one industrial source to another. As a result it is not easy to choose a general treatment suitable for the different types of cutting oils. In this work the description and operation of a pilot plant, involving several operations, for the treatment of spent emulsified cutting oils is reported. 2. Modular pilot plant description The design and construction of a modular pilot plant for the treatment of oil-containing wastewaters, which offers the possibility of combining different treatments, was carried out for the following process parameters: feed capacity 300 L/h, oil content 0.110 vol % and suspended solids 500 1000 mg/L. It was decided to build a small-size plant, so that it can be easily transported to sources where the oily wastes are generated. A suitable spent cutting-oils treatment consists of three basic steps: primary, secondary and tertiary treatment, as shown in Fig. 1. The design should allow the combination of several treatment

FREE OILS

SOLUBLE OILS AND ADDITIVES

OILY WASTEWATER

PRIMARY TREATMENT

SECONDARY TREATMENT

TERTIARY TREATMENT

AQUEOUS EFFLUENT

DISPOSAL METALLIC FILINGS

RECYCLING

OILY SLUDGES

RECOVERY

DEHYDRATION

Fig. 1. General process for the treatment of spent cutting oils.

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operations, depending on the nature of the stream to be treated. The entire process should be automatically controlled using a specific computer software. With these principles in mind a modular plant was built and its schematic diagram is shown in Fig. 2. The experimental configuration is now described in more detail. 2.1. Filtration Suspended solid particles are removed in the primary treatment by filtration. The solids content in oily wastewaters is usually low, but solid particles must be removed in order to avoid abrasion and deposition problems in different parts of the plant. Two kinds of filters were installed. A magnetic filter was used first to remove metal filings, entrained with the cutting oil, and polarized particles. The effluent could then be passed either through a mesh or sand filter to remove the non-magnetic particles. A mesh filter was chosen, because of its easy cleaning, with a 100 m mesh size, resulting in a final stream with less than 0.1% of the initial solids content.

2.2. Feed holding tank A 1000-L feed holding tank, constructed with stainless steel, was used to store the waste oily water, so that the plant could be operated in a continuous mode. The tank has two outlets, through a 3-way valve, for two possible treatment lines: demulsification/ centrifugation and peat bed filtration. It also includes an outlet at the bottom of the tank to remove settled solids, which might pass through the two previous filters. If the selected treatment for the wastewater is demulsification/centrifugation, the wastewater stream must be heated up to 50C, using three electrical heating devices inside the tank, which heat the feed in a short time. 2.3. Demulsification/centrifugation This stage is selected for the treatment of mineral and semi-synthetic cutting oils. Free oil removal, emulsion breaking and partial emulsified oil removal using this treatment can be achieved. Splitting of the oil and water phases requires the addition of chemicals at a certain concentration,

FILTRATION AS PRETREATMENT

MODULE # 4

DEMULSIFICATION/ CENTRIFUGATION

MODULE # 1
ULTRAFILTRATION

FEED TANK

MODULE # 2

PEAT BED FILTRATION

MODULE # 5

MODULE # 3

Fig. 2. Schematic diagram of the modular pilot plant for the treatment of oil-containing wastewaters.

J.M. Benito et al. / Desalination 147 (2002) 510

added with a dosing pump in an intermediate tank. A non-toxic biodegradable organic demulsifying agent, WS009 (Alfa Laval), which completely breaks the emulsion, was selected. The demulsifying agent action requires a certain residence time obtained through a recirculation loop. Once the emulsion has been broken down, the stream is sent to the centrifuge, which speeds up the separation of the two phases. The oil removed is collected in a container and it is possible to burn it in a thermal power plant, if the water content is low enough. The centrifuged aqueous stream is fed to the ultrafiltration module. 2.4. Ultrafiltration Ultrafiltration is the membrane technique used in this plant to remove the remaining oil in the aqueous phase, after >95% of the oil has been removed in the previous steps. Two streams were obtained in this stage: a permeate with a very low oil content, and an oil rich retentate. Ultrafiltration was selected instead of microfiltration to avoid any colloidal oil permeation across the membrane pores. A tubular ceramic membrane Membralox, supplied by Societ des Ceramiques Techniques (SCT, Tarbes, France), was selected due to its high chemical resistance. This membrane is a composite of microporous zirconia (ZrO2) on -Al2O3, with a pore diameter of 50 nm. Its configuration is of tubular multichannel membranes module (7 membranes with 19 channels), with a total membrane area of 1.7 m2. A backpulsing system was used to reduce fouling, due to the deposition of oil and other compounds on the membrane surface, which periodically sends a high-pressure permeate flux in the opposite operational direction. 2.5. Peat bed filtration If the spent cutting oil to be treated is a synthetic one or if the permeate obtained in the ultrafiltration stage has an oil content higher than the limiting standards, a peat bed filter is used.

This filter retains the oil as a result of a combined mechanism of adsorption, coalescence and coagulation. Before its use, the peat is washed with running tap water and air dried till constant weight and then oven dried for 24 h at 50C. Mixed inorganic salt-peat beds are used, by addition of CaCl2 or CaSO4.2H2O. The equipment used is a plane filter media, with a height of 0.3 m and a diameter of 1 m, with an effective filtration surface of 0.785 m2. 3. Performance of the pilot plant In order to study the performance of this treatment unit, a large volume of waste cutting oil was provided by COGERSA, a waste managing company of Asturias, Spain. This waste cutting oil was originated during the production process of metal components for pumps in a local company. 1600 L of waste fluid after pretreatment had the following characteristics: 30 g per ton of metallic filings Oil content: 22425 mg/L (free-floating oil in the residue was not taken into account as it can be easily removed) COD 65000 mg/L pH 910. The pretreated emulsion was then pumped into the feed storage tank. The emulsion was mixed with 1000 mg/L of the demulsifying agent. Previous laboratory experiments had shown this value was the critical coagulation concentration (CCC) of the emulsion. In order to assist the sedimentation process, the emulsion was fed to a centrifuge and the characteristics of removed oil in this stage were: 30 wt % water 2 wt % chlorine 29500 kJ/kg as combustion heat. The resulting aqueous phase obtained at this point had the following concentrations: 1500 mg/L oil 9000 mg/L COD.

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300

Permeate flux, L/m h

250 200 150 100 50 0 0

v = 1 m/s v = 2 m/s v = 3 m/s

P, bar

Fig. 3. Effect of crossflow velocity on permeate flux for oily emulsion ultrafiltration.

After centrifugation, the effluent was fed to the ultrafiltration unit. The results of the ultrafiltration stage are shown in Fig. 3. It can be observed that there is no effect of the crossflow velocity on the permeate flux up to a transmembrane pressure of 2 bar. Above that value the permeate flux is influenced by concentration polarization and an increase of flow increases the permeate flux. The permeate stream obtained from the ultrafiltration unit had the following characteristics: 500 mg/L oil 8000 mg/L COD. It must be pointed out that this effluent had still high values of COD and oil content. This can be justified by the fact that the oily waste was a mixture of the three types of cutting oils available in the market (mineral, semi-synthetic and synthetic). The permeate obtained had a green color resulting from the dyes, usually added to the cutting oil, or to the blending of a synthetic cutting oil with other machining fluids. Hence, the high COD values observed were related to chemicals, present in the composition of synthetic machining fluids, and not retained by the UF membranes. The oil concentration in the permeate is also high. This oil was not retained because it was not a true emulsion (the permeate was translucent, without turbidity), it was in fact soluble oil, that

did not form droplets, and therefore was not retained by ultrafiltration. In order to obtain an effluent acceptable for discharge the following treatment step was a peat bed filtration. Tests using mixed beds of peat and calcium sulfate were carried out in order to reduce oil content and COD values. The final effluent obtained had an oil concentration of about 30 mg/L and 6500 mg/L COD. The effluent had undergone a color change from green to a pale brown (likely humic acids from the peat) that along the experiment turned into a dark brown, due to the decomposition of the peat material. This is explained by the high pH of this type of fluids. This decomposition gives the effluent a high COD concentration, but the lower values of oil indicate an adsorption of contaminants and a change in the nature of the organic matter dissolved in the liquid. The resulting final effluent is acceptable for discharge into the sewage system in order to be treated in a conventional waste water treatment plant, as the pollutants that could cause operational problems had been removed. Acknowledgments Financial support by the Comisin Interministerial de Ciencia y Tecnologa (CICYT, Spain) and the European Commission by means of project ref.: 1FD97-0870 (European Regional Development Fund) is gratefully acknowledged. References
[1] S.M. Mahdi and R.O. Skld, Surface chemistry aspects on the use of ultrafiltration for the recycling of waterbased synthetic metalworking fluids: component studies, J. Dispersion Sci. Technol., 11(1) (1990) 1 30. [2] J.L. Kenneth, Demulsification: Industrial Applications, Marcel Dekker, New York, 1983. [3] D. Deepak, S.G. Roy, K. Raghavan and S. Mukherjee, Effect of ferric chloride on the separation of miscible oil from waste water, Indian J. Environ. Health, 1 (1988) 4349.

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[4] V.V. Pushkarev, A.G. Yushaminov and S.K. Men, Treatment of Oil-Containing Wastewaters, Allerton Press Inc., New York, 1983. [5] R. Bokotko, J. Hupka, D. Lelinski and J.D. Miller, Separation of oil-containing particles from water in a cyclone flotation machine, Environ. Sci. Res., 51 (1996) 155164. [6] C. Solisio, A. Lodi, A. Converti and M. Del Borghi, Removal of exhausted oils by adsorption on mixed Ca and Mg oxides, Wat. Res., 36 (2002) 899904. [7] F.F. Nazzal and M.R. Wiesner, Microfiltration of oilin-water emulsions, Water Environ. Res., 68(7) (1996)