ISSN: 1579-4377 DEVELOPMENT OF A NOVEL EFFICIENT BIOREACTOR FOR SULPHATE REDUCTION

Merijn Picavet; Henk Dijkman; Cees Buisman

Paques B.V., PO Box 52, 8560 AB BALK, Netherlands, m.picavet@paques.nl

KEYWORDS Acid mine drainage, sulphate reduction, bioreactor, metal sulphide, BEST ABSTRACT In many places in the world (acid) mine drainage is a problem due to toxic metals and high salt concentrations. A new biological technology based on sulphate reduction has been applied successfully on full scale since 1992. This biotechnology can remove metals to ppb levels and sulphate to below 200 ppm. Metals are recovered as metal sulphides and sulphate as elemental sulphur. This technology uses UASB (Upflow Anaerobic Sludge Blanket) reactors for sulphate reduction. These reactors are limited in the activity (typically 1 kg S converted/m3/day) that can be achieved due to relatively poor mixing. Paques has developed a novel bioreactor dedicated to high rate sulphate reduction using organic substances, such as ethanol, as energy source. In the new reactor, the BEST (Bioreactor Enhanced by Separation Technology), higher activities can be reached due to improved biomass retention. Thus, higher upflow velocities can be implemented leading to better reactor hydrodynamics and higher activities. On a pilot scale level this reactor (7 m3) was successfully tested at ViaSystems Mommers, Echt, The Netherlands. Currently, a full-scale sulphate reducing plant using this technology is being built in South Africa for the treatment of acid mine drainage. INTRODUCTION Paques specialises in the development, design and realisation of high rate biotechnological applications for the industry. Technologies for the recovery of metals and for the conversion of a broad range of organic and inorganic compounds are available. Worldwide, some 500 industrial installations using Paques technologies have been constructed since 1982. For the mining and metallurgical industry Paques offers THIOPAQ technology. Recovery of valuable base metals using biogenic H2S, combined removal of sulphate, nitrate and heavy metals, selenium removal and bio sulphur production are examples of applications. To date, some forty THIOPAQ plants are operated, amongst which eight large-scale plants in the chemical, metallurgical and mining industry (Copini (2000), Peters (1999), Ruitenberg (2001), Boonstra (2001), Dijkman (2002)). One of the technologies concerns the biological reduction of sulphate to sulphide using a suitable electron donor, e.g. ethanol:

3SO4 2 + 2CH 3CH 2OH 3HS + 3H 2O + 3HCO3 + CO2

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The sulphide produced can be readily used to precipitate heavy metals as their respective sulphides.

2 HS + Me2+ 2MeS + 2 H +
In this way metals such as zinc and cadmium can precipitated down to very low concentrations. This principle was successfully put into practice in 1992 at zinc refinery Budelco BV, The Netherlands, for the treatment of polluted groundwater (Scheeren et al. (1993)). Here sulphate is reduced using Upflow Anaerobic Sludge Blanket (UASB) reactors. Simultaneously metals are precipitated as metal sulphides and separated using tilted plate settlers (TPS). Figure 1 shows a picture of this water treatment plant.

Figure 1 - Biological groundwater treatment plant at Budelco BV, The Netherlands.

This plant has run without any difficulties at a mean flow of 350 m3/h. Typical analyses of in and effluent are shown in Table 1.
Table 1 - Typical analyses of in and effluent

Compound SO42Zn2+ Cd2+

Unit mg/l mg/l mg/l

Influent 1000 30 0.8

Effluent <200 <0.15 <0.01

However, the size of the reactors is considerable due to the low biological sulphate reducing activity. Typical conversion rates lay around 1 kg S converted/m3/day. The low conversion rates are a consequence of relatively poor mixing. Mixing is achieved by means of liquid upflow through the reactor of typically 1 m/h. The bacteria are retained in the reactor as granular sludge. Both contribute to increased mass transfer limitation from the bulk water to the bacteria limiting the overall conversion rate. Therefore, it seems obvious that improving mixing characteristics could result in higher bioactivities reducing the reactor size considerably. This led to the BEST concept (Bioreactor Enhanced through Separation Technology): A high rate bioreactor dedicated to sulphate reduction. This paper reports on the development of this new reactor from pilot scale to full-scale application.

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DESIGN CONSIDERATIONS Mixing in the UASB reactors is achieved by applying a liquid upflow velocity. This way, mixing is obtained under low shear conditions preserving the granular sludge and thus retaining active biomass in the reactor. Mixing can be improved by increasing the upflow velocity. The most straightforward way is decreasing the reactor surface area at a same volumetric flow rate leading to higher reactors. However, this leads to an increased chance of biomass washout and activity loss. Therefore, improved biomass retention is needed. This can be achieved by equipping the reactor with a tilted plate settler (TPS). The taller reactors are not new. These are the Expanded Granular Sludge Blanket (EGSB) reactors. These are designed for methane production. Adding a TPS to have better biomass retention is new, however, and distinguishes the BEST from the rest. This reactor concept has been developed by Paques and recently put into practice in South Africa for sulphate removal from mine water. The first pilot scale experience, however, stems from 1998 and was carried out at ViaSystems Mommers BV, the Netherlands. PILOT PLANT From March until September 1998 the BEST was tested on a pilot scale level for the treatment of wastewater containing sulphate and metals from ViaSystems Mommers, a factory producing integrated circuits (Picavet (1998)). They treat their water using a physical/chemical treatment plant. Because of more stringent demands by the government and their striving to reuse industrial water, they were looking for new means of treating their water. Biological sulphate reduction and simultaneous metals precipitation as metal sulphides was considered a likely option. At this site 7 different wastewaters were available with a total flow of 80 m3/hr. The mean composition of all the wastewaters combined is shown in Table 2.
Table 2 - Typical analysis of the wastewater

Compound SO42Cu2+ Sn2+ Pb2+ Ni2+ Zn2+

Unit mg/l mg/l mg/l mg/l mg/l mg/l

Influent 840 90 11 15 2 1.5

Figure 2 shows a schematical representation of the pilot plant. The influent flow was set at 1 m3/hr. The influent is fed to a buffer tank. Here, the pH is controlled at 8 and the water is brought to temperature. From the buffer tank water is pumped to the BEST where sulphate is reduced to sulphide using ethanol as an electron donor. Metals present precipitate as their respective metal sulphides. Part of the effluent of the BEST is recycled to the buffer tank to be able to reach a wide range of upflow velocities without overloading the BEST. The rest of the effluent goes to an aerobic reactor where excess sulphide is oxidised to elemental sulphur. The elemental sulphur produced is separated using a tilted plate settler. Part of the sulphur slurry is recycled to the aerobic reactor to preserve biological activity; the rest is discharged. The TPS overflow is polished using a dynamic sand filter. The main advantages envisaged were: Lower residual metal concentrations since they precipitate as their respective sulphides. Very low sulphate concentrations are possible (<500 mg/l). The overall objectives were to test the newly designed anaerobic reactor and prove the abovementioned advantages.

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BEST

Influent

Buffer Tank

Ethanol Nutrients

Aerobic Reactor

TPS
Effluent

Sand Filter

Air

Sulphur Sludge

Figure 2 - Schematical block diagram of the Mommers pilot plant.

RESULTS AND DISCUSSION Sulphate was removed down to concentrations of 400 mg/l, which was well below the effluent demand. Metals removal was satisfactory as well. Typical effluent concentrations of less than 1 mg/l were reached. Mean effluent concentrations are shown in Table 3.
Table 3 - Typical analysis of the process effluent

Compound SO42Cu2+ Sn2+ Pb2+ Ni2+ Zn2+

Unit mg/l mg/l mg/l mg/l mg/l mg/l

Influent 400 < 0.8 < 1.0 < 0.8 < 0.2 < 0.6

Figure 3 shows a photograph of the BEST. The BEST performed according to the expectations. Stable operation was no problem. Upflow velocities as high as 6 m/h could be applied without significant washout of sludge. Thus, the biomass retention was more than satisfactory. Furthermore, this implies that sludge was accumulated inside the BEST. The sludge over the BEST reactor was characterised using four sample points at different heights over the reactor. Table 4 shows the composition at each sample point for samples taken 1.5 months apart. It shows solids accumulated in the BEST over time and mainly resided in the bottom part of the reactor. Both the TSS and VSS concentration increased over time. However, the organic fraction of the sludge decreased showing that most metals sulphides remained in the BEST and contributed to pellet formation. This is confirmed by the fact that practically no suspended solids were washed out. The organic fraction was the lowest at the bottom. Since no significant washout was noticed, eventual sludge discharge is best done from the lower part of the reactor.

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Figure 3 - Pilot plant at Mommers with the BEST at the back.

Table 4 - Sludge characterisation of BEST sludge at different heights.

Sample point 11) Sample point 2 Sample point 3 Sample point 4 Mean over BEST

Sample at t = 0 VSS TSS (kg/m3)2) (kg/m3)3) 67 46 19 14 0 0 0.6 0.1 21 14

Sample at t = 1.5 months TSS VSS (kg/m3) (kg/m3) 106 47 57 35 0 0 0 0 42 22

1) Lowest sample point 2) Total Suspended Solids 3) Volatile Suspended Solids

One of the essential features of the BEST is increased biological activity compared to UASB reactors leading to smaller reactors. The pilot reactor showed that this is possible using the BEST. The increased upflow velocity led to at least a doubling in the sulphate reducing activity compared to a standard UASB. Next to the upflow, important parameters influencing the activity appeared to be the pH and a high enough sulphide concentration. The preferred sulphide concentration lay between 200 and 500 mg/l. In this range, methanogenic activity is inhibited and sulphidogenic activity induced leading to efficient electron donor usage. Metal sulphides precipitation might interfere with biological activity due to encapsulation of the biomass. Such problems were not encountered during this pilot experiment. FULL SCALE PLANT Since the first BEST pilot experiment more pilot projects were run on a smaller scale. One of these projects has led to the actual implementation on a full-scale level. At the moment, the first full scale BEST is started up in South Africa. CONCLUSIONS Paques has developed a novel reactor, the BEST, specific for biological sulphate reduction using organic electron donors. Pilot experiments have shown that higher sulphidogenic activities are achievable than with UASB reactors due to better mixing. Furthermore, methanogenic activity is limited due to

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operation at relatively high sulphide concentration. Thus a more efficient process is achieved, since the electron donor is mainly used for sulphate reduction. Metals precipitation in the BEST showed to be no problem. REFERENCES Boonstra, J., Dijkman, H. and Buisman, C.J.N., 2001. Novel Technology for the Selective Recovery of Base Metals, Waste Processing and Recycling in Mineral and Metallurgical Industries IV, Eds. S.R. Rao et al., MetSoc, pp. 317-323. Copini, C.F.M. et al., 2000. Recovery of sulfides from sulfate containing bleed streams using a biological process, Lead-Zinc 2000, Eds. J.E. Dutrizac et al, TMS, pp. 891-901. Dijkman, H. et al., 2002. Optimization of metallurgical processes using high rate biotechnology, Sulfide Smelting 2002, Eds. R.L. Stephens and H.Y. Sohn, TMS, pp. 113-123. Peters, A.S., 1999. The Selective Removal of Copper and Arsenic from Electrolyte Bleed Development and Design of a Sulfide Precipitation Process, (confidential), nr. PM88.02.005. Picavet, M.A., 1998. Biologische zuivering van afvalwater afkomstig van de printplatenindustrie, confidential internal report about pilot project (confidential). Ruitenberg, R. et al.,2001. Copper electrolyte purification with biogenic sulfide, Electrometallurgy 2001, Eds. J.A. Gonzales et al., MetSoc, 2001, 33-43. Scheeren, P.J.H., Koch, R.O. and Buisman, C.J.N., 1993. Geohydrological Containment System and Microbial Water Treatment Plant for Metal-Contaminated Groundwater at Budelco, World Zinc 93, Hobart, Tasmania, October 10-13, 373-384.

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