DESALINATION ELSEVIER

Desalination 106 (1996) 145-150

A water treatment and recovery plant for highly acidic heavy metal laden effluents
V. Cinanni*, I.A. Gough, A.J. Sciuto
Tel +61 (9) 956-8222; FOX +61 (9) %%-8233 RGC Mineral Sands Ltd., PO Box 62, Geraldton 6530. Australia.

Received 20 March 1995; Accepted 20 June 1995

Abstract RGC Mineral Sands Ltd. has developed and operated a prototype water treatment and recovery facility at Geraldton for the past 7 y. It is a stand-alone facility capable of treating a wide variety of acidic industrial effluents and ground waters. Water recovery in excess of 90% is readily achievable, and near potable water (with respect to TDS) is produced. All streams are successfully contained and sludge is stored in synthetic lined solar

evaporation dams in accordance with a zero discharge policy. This paper describes the operating experiences and practices developed for the process, which at the time of commissioning (March 1987) was considered unique, and to the authors knowledge the only one in Australia with this combination of features.
Keyworuk: Industrial effluents; Water recovery; Heavy metals

1. Introduction
rutile

RGC Mineral Sands Ltd. operates synthetic (SR) plants utilizing the Becher process at Cape1 and Geraldton in Western Australia. This involves the high temperature reduction of ilmenite followed by oxidative leaching of metallic iron and a final sulphuric acid leach to remove residual levels of iron and manganese. The effluent from the acid leach is treated and recovered in a stand-alone water treatment and recovery facility developed by RGC over the past 7 y.

*Corresponding

author.

Development of this facility commenced in 1985 when Western Titanium Ltd. (WTL), an engineering project services branch of RGC Mineral Sands Ltd., set out to research, design and develop a 35 m3/h fully integrated water treatment and recovery facility (WT) for their newly proposed SR plant at Geraldton, Western Australia. At the time RGC operated the only direct reduction SR plant in the world at Cape1 (WA) and owned the patented Becher process. Initial research and development was carried out on a small-scale batch pilot plant at Capel. The Geraldton SR plant was to be a two-fold scale up of the Cape1 SR plant and the WT facility built to

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V. Cinanni et al. 1 Desalination 106 (1996) 145-150 Table 1 Typical composition

suit that capacity (35 m3/h). In 1991 RGC further doubled its SR operations in Geraldton and the water treatment and recovery facility was rebuilt to a capacity of 94 m3/h. The effluent is typically at pH 1.5-2.0 and contains predominantly FeSO, and MnS04 with minor levels of NaCl and NH&l and trace levels of heavy metals. The liquor also contains sediment of ultrafine SR and iron oxides. The process involves the lime-soda ash system followed by microfiltration (MF) and reverse osmosis (RO). Sludge dewatering allows water recovery to reach over 92.5% and storage of the neutralized sludge cake in synthetic lined dams or other acceptable uses.

of raw effluent and product water

Raw acid
effluent PH Eh, mV TSS, g/l Cations: (mgil) H+ NH; Na+ K+ Ca*+ Mg*+
MnZt Fe* Co, Ni, Cu, Cr, Ba, Sr

Product water 6.5 0

2.0 350 up to 1.0

10.0 630 500 15 50 30

800 8,000 <5 (trace)

0 40 120 2 0 0
0 0 0

2. Site environmental

policy

Anions: (mg/l)
Clso;NOPO,? HCO, SiO, Total dissolved salts, mg/l 1,980 15,550 10 1 0 20 27,595 120 120 0 0 100 0 500

The RGC environmental policy encompasses a genera1 philosophy of maintaining or improving the environment it operates within, and as such the plant design for the proposed water treatment and recovery plant required total containment and zero discharge criteria.

3. Objectives The objectives of the project were to (1) neutralize continuous large volumes of highly acidic effluent (pH 1.5-2.0) laden with heavy metals; (2) remove heavy metals from liquors and store in a stable form (sludge); (3) produce a near potable product water for recycling, thereby reducing process water requirements for the SR plant; and (4) ensure no environmental impact on the adjacent agricultural and grazing lands. 4. I, Neutralization The heavy metals are removed by simple lime precipitation reactions at pH 10.0 or higher. Transition metals such as manganese require a higher pH of 10.5 to allow precipitation of manganese to below 0.1 ppm, together with iron and most other heavy metals that might be present. The sludge is settled with flocculent in the primary clarifier, and the underflow is dewatered and sent to the evaporation dams. Lime is supplied in bulk and slaked in a 5 tph unit on site. CaC03 is recycled in part from the carbonation section to supplement lime addition, reducing the lime requirements. The main reactions are: FeS04 +Ca(OH), + Fe(OH& (4) + CaS04 (1)

4. Process chemistry The raw acid effluent has a typical composition shown in Table 1. Fig. 1 is a simplified representation of the process which can be described by the following steps:

V. Cinanni et al. / Desalination IO6 (1996) 145-150

AC,0

147

ACID LEACH

NEUTRALISATION FmcCLENT _____) *NmCAEN, .-* * pn m.5

(SLUDGE Dl li.qO,

WITER TREATMENT

.
1 MICROFILTRATION ]

cocnllt*

[ REVERSE OSMOSIST--------_
WATER RECOVERY

.__J

Fig. 1. Schematic of water treatment and plant at recovery RGC, Geraldton.

MnSO,+Ca(OH), H2S04+Ca(OH), H2S04+CaC0,

-+ Mn(OH)2 (&) + CaSO, + 2H20+CaS0 4 (k) + H,O+CO, (?) +CaSO, (4)

(2) (3) (4)

4.2. Carbonation This is essentially a soda softening stage, removing soluble calcium to below 10 mg/l from solution which might otherwise produce gypsum scale in piping, vessels and membranes downstream. Soda ash is supplied in bulk. CaSO, + Na+.ZO, + CaC03 (4) + Na$O, (5)

Calcium sulphate will reach supersaturation in Eqs. (l)-(4) and crystallize as gypsum and report to the sludge. It is not uncommon to have up to 30% of the sludge as gypsum. Fig. 2 illustrates the pH range at which various metal hydroxides precipitate as calculated from suitable equilibrium constants [ 11.

The calcium carbonate precipitate is settled in the secondary clarifier and re-utilized for one of two purposes: (a) recycling to neutralization in place of lime addition, thereby reducing lime

V. Cinanni et al. / Desalination 106 (1996) 145-150

Fig. 2. Solubility curves -

hydroxides. 4.3. Microfiltration The purpose of this unit is to provide the desalination unit with sediment-free liquor, free of organic and particulate matter (e.g., oil, flocculants, calcium carbonate, debris). It is essentially a physical separation process, and several types of microfiltration units are available for this application. A cross-flow microfiltration (CFMF) curtain unit was specifically developed and modified for this process because of its simplicity of operation and generally lower capital and operating costs. The vendor, Hitech Water Pty. Ltd., is a locally owned company. The CFMF curtain system has the advantage of not requiring a backflush and operating at low pressures (cl00 KPa). All liquors are recycled until acceptable permeate quality is achieved, thereby providing 100% water recovery from this section. Other alternatives are available today which may be suitable for this process. The principle of operation in the curtain unit is based upon the substrate forming its own dynamic filter inside the woven cloth curtain

usage, and (b) seeding requirements in the carbonation section. The carbonation reaction is relatively slow. Seeding with CaC03 provides a significant advantage to the formation of well sized crystals, which then promote better settling and filtration characteristics in the proceeding stages. The level of soluble calcium can be increased by several variables including: high TDS levels in the presence of 2,000 mg/l (Na++Cl-), the (Ca*+ + SOi-) concentration increases from 2,100 to 2500 mg/l (i.e., 12%) lower sulphate levels temperature and other physical parameters presence of NH: ions which also increase CaSO, solubility A detailed treatise of the chemistry of limesoda softening aspects is covered in [2] and [3]. The above variables are a function of the effluent quality and have an effect on the soda ash requirements for the process, soda ash being the most expensive reagent in the process.

V, Cinanni et al. / Desalination 106 (1996) 14.5-150 tubes, therefore filtering to whatever the particle size is at the time. The operation of the CFMF unit does offer some challenges. These are: (a) variable permeate quality with time, (b) variable flux rate with time, and (c) potential chemical scaling if pretreatment is not adequately controlled (e.g., gypsum, sludge, or flocculent blinding). The CMFM unit provides upstream protection for the more expensive desalination unit (RO) and can be cleaned of scale or fouling. On-line monitoring of turbidity and specific ions (Ca2+, Na+) is used to provide automatic operation of this section. The required permeate quality is ~0.1 NTU and ~3.0 on the Silt Density Index a prerequisite for RO feedwater. 4.4. Reverse osmosis This is essentially a desalination operation for sodium sulphate [Eq. (5)] with some sodium chloride and ammonium chloride. Several proprietary units and operating equipment manufacturers are available in Australia today. The main type of membrane used is the spiral wound. The two main forms of this are (a) cellulose acetate and (b) thin-film composite (polyamide or PVD). The water recovery potential from this section is dependent on the salt species and their concentrations which determine osmotic and system pressure. This plant was designed for an overall water recovery of 94% with a 98% salt rejection or higher. Seawater grade membranes have been used successfully in this plant. Sequestering agents are dosed as a precautionary measure against chemical scales (e.g., gypsum, iron and manganese hydroxides). Hypochlorite is dosed for protection against micro-organisms if the membranes are of the cellulose acetate form. pH control may also be required if using the cellulose acetate membranes, as they are suited to a tight pH range of 4.5-6.2 only. Hydrolysis of the membranes may occur outside of this pH range. Sodium metabisulphite is dosed to guard against oxidation of polyamide membrane. 4.5. Sludge dewatering

149

The existing process uses belt presses that are fed from the primary clarifier underflow. Sludge cake moisture is typically 40-50%. Where higher levels of dewatering are required, moisture levels of 10% can be achieved with high pressure units, though operating and maintenance costs increase. Alternatives to the belt press include the tube press and ceramic drum filter. Centrifuges have also recently been used with some success in the water treatment industry. Alternately, the sludge is settled in the lined dams directly and the decant liquor recovered to the carbonation system. Flocculent is used to enhance the dewatering process. 4.6. Evaporation dams Double-lined evaporation dams have been operated effectively over the past 7 y. The linings are generally of HDPE, though PVC and Hyperlon linings are also used. There is a matrix of leak detection pipes in between the linings and inspection sumps to detect any ruptures in the linings. The dams are designed for a life expectancy of between l-3 y. 4.7. Lime slaking Lime (calcined lime sand) is slaked on site in a 5 tph slaker. The efficient slaking of lime is essential, otherwise an excess of sludge (unreacted lime) is produced and treatment costs increase. Lime particle size is also a factor, as coarse particles of slaked lime will tend not to wet up as well and be poisoned on the surface by gypsum. Lime slaking efficiency curves are required to determine the optimum temperature and throughput at which to run the slaker. This optimum operating condition will be different for alternate lime sources. The use of milled lime improves the efficiency of slaking and eliminates the need for grits removal prior to neutralization. Alternatives to slaking may be available if economics

prevail. These include (a) the supply of prepared milk of iime from existing lime slaking facilities and (b) the supply of quick lime (preslaked/milled lime) which reduces capital costs. 4.8. Soda ash Soda ash is premixed in an agitated tank and made up to 15-20 wt%. The sole concern here is the solubitity of Na,CO, at lower temperatures. Where ambient temperatures of less than 15C are experienced, it is recommended that 15 wt% solutions are used so that recrystallization in piping does not occur. 4.9. Flocculation The flocculent type needs to be optimized according to sludge characteristics and may also be limited by the RO membranes, which may succumb to flocculent blinding. Anionic flocculants are preferred because they are charge repelled by the RO membranes active surface. Flocculants are used typically in three locations: 1. settling of neutralized sludge in primary clarifier (@ 6 mg flocll effluent) 2. dewatering of sludge from primary clarifier underflow (@ 1 Kg floe/tonne solids) 3. settling of calcium carbonate in the secondary clarifier after soda ash addition.

sealants may also be used here. An annual shutdown is generally sufficient for cleaning and descaling of the lime reactors. Corrosion potential is high and requires careful materials selection. This plant has used stainless steel and ABS piping with rubber lining and epoxy coatings in vessels. The main area of concern is that associated with the acidic effluent, though salt corrosion ~roughout the circuit is evident.

6. Conclusions RGC Mineral Sands Ltd. has developed and operated a prototype water treatment and recovery facility at Geraldton over the past 7 y with considerable success. In essence it is a standalone facility capable of treating a wide variety of acidic industrial effluents and recovering over 90% of the water at near potable water quality. Ail streams are successfully contained and sludge is stored in lined evaporation dams. Operating and maintenance costs are reasonable, though training requirements are high due to the pretreatment chemistry involved and the hi-tech area of RO.

7. Acknowledgements The authors wish to ac~owledge the permission of RGC Mineral Sands Ltd. in publishing this paper on a subject of interest not only to the mining industry but also any enviro~en~lly conscious management.

5. Plant performance Operator and routine maintenance costs are typical for such plant equipment. However, training costs would be a factor as the level of technical understanding required by the operator in this section is considerable. The plant is run by one part-time operator per shift and an overseeing technician. The greatest potential for scale is in the lime addition reactors (i.e., gypsum), and to a lesser extent in carbonation and MF. The latter will only occur if soda ash is underdosed. Anti-

References
G.H. Aylward and T.J. Findlay, SI Chemical Data Book, 2nd ed., Jacaranda-Wiley, 1979. PI W. Stuum and J.J. Morgan, Aquatic Chemistry, 2nd ed., Wiley Interscience, New York, 1981. II31 F.N. Kemmer, Nalco Water Handbook, 2nd ed., McGraw-Hill, New York, 1988.

PI