The
second question should be, "Which technologies are in common
use?" If a process is in widespread use, it has passed the
test of time with others and is cost-effective. Next comes a determination
of whether or not this process is technically feasible at the plant.
This step may require months of bench scale and pilot testing to
develop a comfort level. If this testing is positive, the search
is done, and it is time to move to the design phase. If the testing
does not prove a common technology, then facilities need to move
into the newer technologies, such as membranes.
Evaluate
Conservation
In the early 1980s, when the original metal finishing wastewater
regulations were promulgated, the following steps were typically
followed:
Step
1: Shop for wastewater equipment.
Step 2: Get sticker shock.
Step 3: Consider water and chemical conservation methods
to reduce the capital and operating cost of the wastewater equipment.
Step 4: Shop for wastewater equipment with reduced chemical
loadings and flow rates.
Why
not eliminate Steps 1 and 2 and proceed directly to Step 3? There
is no reason for equipment shopping or sticker shock when you can
reduce the cost of wastewater treatment through water and chemical
conservation. Reducing water and chemical consumption by 25-50 %
is commonplace.
The
list of potential cost savings is endless, but consider the following:
- Reducing
rinse water flow rates with automatic valves controlled by conductivity
sensors. Conductivity sensors are much more reliable than in the
past.
- Use
RO water for all metal finishing uses. Many plants use unreasonably
high amounts of water to compensate for poor water quality. RO
equipment has dropped considerably in price as the technology
has become widespread in industrial and commercial applications.
-
Automatic chemical feeders, particularly for use with liquid alkaline
cleaners, can produce cost savings. Typically, without automatic
feeders, operators renew the bath at the beginning of the shift,
and the bath is made very stout to last the entire shift. With
automatic feeders, constant feed of chemicals results in less
chemical usage.
Consider
Modifications or Replacement of the Existing System
After conservation methods, the most cost-effective approach
is to modify your current treatment system. Many metal finishers,
however, will simply replace their wastewater plant built in the
'80s that has outlived its useful life due to corrosion and an outdated
relay-logic control panel. The following technologies should be
considered. The cost-effectiveness of these technologies varies
with your situation and often other constraints, such as available
space, will dictate the solution.
- Ferrous
iron co-precipitation is often more effective and typically less
costly to operate than a hydroxide based system. Ferrous iron
co-precipitation can be used to either replace the current hydroxide-based
system or as a polishing step to the hydroxide-based system. These
systems are well proven to meet very low metals limits, often
less than 20 ppb of the individual metals. In addition, hexavalent
chromium is reduced and co-precipitated along with other metals.
This technology forms a dense iron sludge that physically entraps
containments as it is formed. The system is effective in the presence
of chelators and oils since they are caught up in the matrix.
Modifying an existing system consists of replacing the existing
pH adjustment tank with a special reactor and modifying the system's
control sequence per the supplier's recommendations. A new reactor
and clarifier are required to use this technology as a polisher
to an existing hydroxide system.
- Chemical
additives may be added to existing precipitation systems to reduce
metals below their hydroxide solubility limits. These chemicals
have become widespread. These compounds are typically sold as
liquids and metered in at the pH adjustment tank. Dithiocarbamate
(DTC) forms an insoluble metal sulfide precipitate and is particularly
useful in removing metals from chelating agents such as ethylenediamine
tetracetic acid (EDTA). DTC forms a double bond with metals that
is much stronger than the bond between chelants and metals. DTC's
attraction is so strong that it physically removes the metals
from the chelant's weak grasp. The main drawback of DTC, however,
is the toxicity of its breakdown products that should be evaluated
fully prior to implementation. Chemical suppliers also have a
number of other products including chelating polymers that scavenge
the soluble metals in a hydroxide-based system.
- Membrane
systems continue to improve in performance and have lower capital
costs. Ultrafiltration (UF) systems are fine filters that may
reduce metals concentrations by removing total suspended solids
to low levels. Dissolved metals are typically not removed beyond
the metal hydroxide solubility limits by UF. UF is widespread
in metal finishing and oily wastewater treatment, and membrane
life is much less of a worry than it was 10 years ago. Nanofiltration
and RO are much less widespread and should be considered in the
development stage for wastewater treatment. Nanofiltration will
physically reject divalent metal ions as well as cations such
as sulfates. RO will produce effluent with metals at the analytical
detection limits, but it is the riskiest and costliest technology
available. The shortcoming on all membrane systems has been in
membrane life, and only pilot plant testing can prove the technology
for your application. The cost of this testing, however, may be
very worthwhile since wastewater treated by membranes may be suitable
for recycle.
- Ion
exchange systems may be used as stand-alone treatment or as polishers
to existing hydroxide-based systems. Ion exchange systems will
meet low levels and may render a wastewater suitable for reuse.
The water must be filtered to avoid physically plugging the ion
exchange vessel. The technology consists of passing the water
through a pressurized vessel filled with ion exchange media. Dissolved
metal ions replace hydrogen ions on the surface of the media.
The systems are regenerated with an acid solution and concentrated
metal-bearing brine is produced. Most ion exchange systems are
regenerated on-site and the brine is typically hauled to a hazardous
wastewater treatment facility. Evaporation of the brine may be
used to reduce the volume hauled.
Examples
The following two examples demonstrate the process of selecting
treatment technologies.
Problem
1: A metal finisher has a 20 year old, 200-gpm hydroxide treatment
system that uses the additive DTC to meet NPDES limits. Approximately
1,000 mg/liter of calcium chloride is also added to control oil.
The system is in excellent physical condition, and the plant recently
updated its system with a new state-of-the art control panel. The
current DTC cost is $32,000 per year and would have doubled to more
than $60,000 if it had had to comply the new MP&M regulations.
The plant's environmental manager is concerned about increasing
DTC usage because the effluent has occasionally failed aquatic toxicity
limits. Physical space is at a premium and the plant manager wishes
to know if there is a simple process change that is more cost-effective
and eliminates DTC usage.
Solution:
The least intrusive change would be to increase chemical additives,
but DTC was the only compound that was effective during jar testing.
A ferrous iron co-precipitation system will not require a building
addition, but rather a simple changeout of the pH control tank to
a specially designed reactor. The new control system is PLC controlled
and could be modified to accommodate this change.
Jar
testing demonstrated compliance with a ferrous dosage of 600 mg/liter
and no DTC or calcium chloride. Annual cost savings in chemicals
was projected at approximately $90,000 per year with a savings of
approximately $10,000 per year in sludge generation. The installed
capital cost of the reactor is $55,000 and can be installed during
a short production shutdown. The plant has budgeted the conversion
during a holiday shutdown rather than wait for the upcoming regulations.
Problem
2: A manufacturer of electronic components has a 25-year-old,
sodium hydroxide precipitation system treating 50 gpm of waste containing
lead, copper, and nickel. Five years ago, a sand filter was added
to improve its compliance record with the existing metal finishing
standards. The existing treatment system is in poor condition, with
extensive corrosion of the process equipment as well as the control
panel. Plant management desires a highly reliable, cost-effective
system that requires minimal maintenance and management and is open
to the idea of a new system. The plant has room for a small treatment
system and space for a building addition.
Solution:
A survey of the manufacturing equipment showed that one of the printed
circuit board etchers produced as much metals in its waste stream
as the other three etchers combined. It was decided to perform the
wastewater evaluation assuming that this machine was replaced with
a more efficient unit. The revised waste stream was projected to
have a total metals content of approximately 20 mg/liter versus
the previous 50 mg/liter at a reduced flow rate of 30 gpm.
Bench
scale testing showed that ferrous iron co-precipitation as well
as hydroxide precipitation with DTC addition could meet requirements.
Ion exchange was tested and found to meet the limits. A cost comparison
was made between a new precipitation system and ion exchange with
both on-site and off-site regeneration. The installed capital costs
and operating costs were estimated as follows:
|
Capital
Cost
|
Annual
Operating
|
Ferrous
iron co-precipitation |
$350,000
|
$65,000
|
Hydroxide
precipitation with DTC |
$325,000
|
$70,000
|
Ion
exchange with on-site regeneration and brine evaporator |
$250,000
|
$40,000
|
Ion
exchange with off-site regeneration |
$50,000
|
$60,000
|
The
evaluation team selected the ion exchange with off-site regeneration
system since it greatly minimizes wastewater treatment labor, provides
a high level of treatment, and requires minimal capital investment
since the ion exchange contactors are leased.
Planning
for an efficient and cost-effective system should never be put off.
It requires time to evaluate and implement both conservation efforts
and new wastewater treatment technologies.