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• many tanks and storage for effluents, chemicals, sludge, reactors for mixing of
effluents and reagents of both treatments and pre/post-treatments
• a large volume setter
• a plate filter press
• many pumps
• control and regulation systems of important parameters, e.g. pH and Redox potential
The control of effluents requires many measurement instruments and frequent analyses. If the
treatment is accurately carried out, it allows to respect the in force regulations. The content of
organic material, measured through the COD -Chemical Oxygen Demand, in the effluent is
often higher than the allowed maximum limit, and also effluent salinity is high.
When the salt content is low, rinsing waters can be recycled through mobile columns (1)
with ionic exchange resins. Concentrated effluents, coming from exhaust baths and static
rinsing, wlll be conferred to authorized places for their treatment (figure 2).
When the salt content is high, the use of columns with ionic exchange resins is substituted
for a flxed installation of ionic exchange, with regeneration of the columns within the surface
treatment shops. Exhaust baths will be conferred to authorized companies for disposal.
Concentrated wastes from static rinsing and eluents of regeneration resins usually are
characterized by large volume, requiring concentration by evaporation in order to reduce
transportation costs and disposal at authorized sites. The distillate from evaporation can be
recycled and reused in the production process (figure 3).
Fig. 3 - Series of treatment of the rinsing waters when low and salt content are very high
It must be noted that the regeneration of ionic exchange resins can become a frequent
maintenance operation and a heavy duty for the treatment shops.
If flow and salt content are very high, it becomes necessary the opportunity of specific
treatment for each rinsing station.
Let us consider an intermediate situation, in which the treatment through ionic exchange is
too much demanding but rinsing flows are not so important to justify individual station
treatment.
4. Study of the intermediate condition (neither ionic exchange nor individual station
treatment)
The basic of the treatment is reported in figure 4.
Concentration can be carried out through evaporation or inverse osmosis. Problems are
nonetheless
where:
n = number of rinsing water tanks
C0 = concentration in the treatment bath
C'0,= concentration in the static bath which comes before the sequence of counter-flow
rinsing tanks
Cn= concentration of the last rinsing tank
The concentration Cn is defined by the required qualiiy for rinsing (C0/ Cn = 10.000). For
example, if C'0 = C0 /5, the flow Q for the first reported sequence is 6.7 m3 and for the
second is 1.1 m3. The flow is reduced of a factor of six, from the first to the second sequence.
Mixing of effluents
Effluent flows are very different among each other in a traditional surface treatment shop.
There are effluents from
• degreasing
• metching
• electrolytic of chemical deposition bath
• post-treatments
These effluents can be acid, neutra1 or alkaline, can contain chemicals which can react if
mixed and generate toxic compounds (e.g. cyanide acid) or solid materials which modify the
concentration (precipitates,...). In order to avoid these problems, two separate flows, one acid
and the other alkaline, are generally used
In figure 6 the process flow of the water treatment through evaporation is reported. ICosts for
evaporation, due to the required characteristics, are generally high:
Fig. 7 - Process flow of the rinsing water treatment through inverse osmosis
In figure 7 the process flow of the rinsing water treatment through inverse osmosis is
reported. Inverse osmosis is a technique which employs special organic membranes, able to
hold ionic substances and small organic molecules, with rejection ratio, Tr, of almost 95%
(Tr = 1 -Cp/Co where Cp: permeate concetration and Co: feed concentratlon). Membranes
are organic polymers. As a function of their chemical nature, they can work at high
temperatures (70° C), at interesting pressure (for some membranes higher than 50 bar) and at
pH between 2 and 11. They are sensible to oxidant agents. The permeate flows, for pure
water, are proportional to the difference of pressure on the two sides of the lateral wall and
membrane surface.
Q = KS (Δp)
For a solution containing electrolytes, the equation reported above is modified in order to
take into account the osmotic pressures on the two sides of the membrane:
Q = KS (Δp - Δpi)
There are a lot of issues with inverse osmosis. It is necessary to operate with:
• large surface membrane, due to the fact that permeate specific flow are low (from 10
to 20 l m2). In most cases; modules have a spira1 shape, a solution which offers the
advantage of the high compactness.
• high working pressures (20 bar) above the osmotic pressure
• continuous cooling of the solutions
Membrane obstruction, due to suspended solids, precipitates or crystallized products during
the treatment, must be absolutely avoided. It is therefore necessary:
Due to the rejection ratios between 0.95 and 0.97, depuration is never complete and the
inverse osmosis system must be at least with two steps (figure 8). Final purification actions
are also required to guarantee the desired characteristics of the permeate to be reused.
Conclusion
Zero liquid discharge is technically achievable through concentration by evaporation or
inverse osmosis, as long as they are coupled with suitable pre- and post- treatment. The use of
these techniques avoids the application of the expensive classic treatment and release the
manufacturer from many legislative dues. Zero discharge implies the production of relevant
volumes of waste which can not be easily valued and whose treatment is very expensive,
even if performed out of the company by specialized and authorized companies.
The design of farms, plants and working methods must be rethinking in order to reduce the
rinsing flow, keeping high standard of quality. It is necessary to study:
• all the possibilities for recycling drag out to treatment baths, without compromising
performances
• all the techniques which allow the depuration of the baths to increase their life and
usage
• all the possibilities to enhance the value the different waste products
Economical feasibility of zero discharge is hard to define, due to the high investment and
maintenance costs.