Fundamentals of Zero Liquid Discharge System Design

Power plants often produce wastewaters that contain salts, such as those from wet gas
scrubbing, coal pile run-off, and leachate from gypsum stacks. Evaporation of those
liquid wastes in a modern zero liquid discharge system produces clean water that is
recycled into the plant plus a solid product suitable for landfill disposal. Here are the
options to consider.

In most power plants, the largest wastewater producer is the cooling water system.
Historically, natural evaporation of the cooling tower blowdown from holding ponds has
been very successful, particularly in the western U.S. This approach to waste liquid
disposal is a simple but effective example of a zero liquid discharge (ZLD) system. The
downside is that the water is permanently lost from the system through natural
evaporation, and the remaining residue must be periodically cleaned from the pond.

Because cooling tower blowdown is relatively dilute, generally less than 10,000 mg/L
total dissolved solids (TDS), reverse osmosis (RO) membranes are often used to pre-
concentrate the cooling tower blowdown prior to concentrating the liquid in an
evaporator; the remainder is reduced to solids in a crystallizer. The salts present in
cooling tower blowdown, for example, are usually composed of sodium sulfate and
sodium chloride with small quantities of calcium, magnesium, sulfate, and bicarbonate.
All of these salts can be readily crystallized by evaporation.

However, wastewater from wet flue gas desulfurization (wet FGD) systems and
integrated gasification combined cycle (IGCC) plants contains highly soluble salts, such
as calcium and ammonium chlorides, and certain heavy metal salts, which are not so
easy to crystallize by evaporation. Conventional ZLD evaporation-crystallization
processes for wet FGD and IGCC waste streams require clarification and extensive
pretreatment. Usually, the wastewater must be treated with lime, soda ash, and other
chemicals to replace the calcium, magnesium, ammonium, and heavy metal ions with
sodium ions so that a crystalline solid can be produced. The pretreatment equipment
and chemicals increase the ZLD system footprint as well as the capital cost and system
maintenance requirements.

Burning or gasifying coal or petcoke produces a gas that can contain sulfur dioxide,
hydrochloric acid, hydrofluoric acid, NOx, fly ash, and many other chemical species. In
coal-fired power stations, wet FGD systems are used to remove those pollutants from
the flue gas. Similarly, a gas-scrubbing step is used in most coal and petcoke
gasification processes. Most use wet scrubbing, in which an alkaline agent dissolved in
water reacts with and removes those noxious constituents from the flue gas. Wet FGD
typically requires a continuous blowdown to limit the accumulation of corrosive salts and
suspended solids absorbed from the gas stream.

The composition of wet FGD wastewaters varies widely, although they are primarily
chloride solutions. There may also be a large concentration of nitrate or formate,
depending on the conditions of combustion. The dominant anion in the wastewater
depends on the sorbent used as the reagent in the wet FGD; typically, it is calcium
carbonate (limestone), sodium hydroxide (caustic soda), ammonium hydroxide, calcium
hydroxide (slaked lime), or magnesium hydroxide.

Therefore, wet FGD and IGCC wastewaters are typically solutions of highly soluble salts
such as calcium chloride or sodium formate, usually in the range of 5,000 to 40,000
mg/L TDS. Discharge of these wastewaters is usually regulated due to the presence of
relatively small amounts of toxic contaminants, such as heavy metals, selenium, boron,
and organics. Often, some type of treatment is required to reduce or eliminate these
toxins from the wastewater before discharge to the environment.

Pretreatment Is Often Required

In the power generation industry, treatment for the removal of small concentrations of
regulated inorganic contaminants in wastewater often includes precipitation and settling
processes.

Typically, wastewater is fed to a series of reactor tanks, where heavy metal ions can be
precipitated as insoluble hydroxide and sulfide salts by adding caustic soda or lime, and
sodium sulfide or proprietary organosulfide. Ferric chloride or alum and specialized
polymers are typically added to coagulate the precipitates and form large flocs, which
will quickly settle in a clarifier.

Often, two precipitation/flocculation stages are included, due to the wide variation in the
optimum pH values for the precipitation of the metals present. The settled metal
precipitates are collected from the bottom of the clarifier and filtered. This treatment
process works well to reduce the suspended solids, metals, and acidity in the
wastewater, but it leaves in solution the highly soluble salts, including calcium,
magnesium, sodium, and ammonium combined with chloride and nitrate, as well as any
organic compounds.

Biological treatment prior to discharge can reduce the nitrates, ammonia, organics, and
oxygen demand, as certain bacteria can use these molecules as food, converting them
to water, CO2, and N2. Some bacteria are capable of reducing oxidized anions of certain
toxic metals (such as selenates and arsenates) to the insoluble metal. Common
bacteria used in commercial biological treatment systems, however, do not affect the
concentration of most chloride salts; in fact, wastewaters containing highly soluble
calcium and/or magnesium chloride often must be diluted to avoid killing the bacteria.
Chemical and biological treatment methods also produce costly sludges.

As the rules for discharging wastewater become more stringent, physical, chemical, and
biological treatment methods may not reduce concentrations to the part per trillion levels
required for discharge of some chemical species, such as mercury and selenium.
Membrane-based technologies are often used to recover water in recycle/re-use and
ZLD schemes.

However, membranes are generally limited to the treatment of dilute wastewater

streams. In the case of treating wastewater from wet FGDs, for example, the option of
using RO membranes must be eliminated because the osmotic pressures rise beyond
accepted limits due to the high concentration of dissolved salts (30,000 to 60,000 mg/L).
Once the dissolved salt concentration in wastewater reaches a few percent by weight,
evaporation must be used to achieve further recovery of water and concentration of
salts.

Understand the Process

When the conventional treatment methods discussed above are unable to treat purge
streams high in chlorides, evaporation of the purge stream is favored. The
attractiveness of evaporation as a way to treat wet FGD blowdown is that, in theory, all
of the dissolved species, whether benign, hazardous, or toxic, can be separated
completely from the water. Also, the process produces a stable solid that can be
landfilled, and a high-quality distilled water is returned for reuse in the plant.

The first steps in the evaporation process are chemical addition (feed tank), preheating
(feed preheater), deaeration, and primary evaporation (brine concentrator), as shown in
Figure 1.

1. Evaporation process. Most of the water evaporation occurs in a falling film

evaporator (inside the brine concentrator vessel) that is seeded with calcium sulfate

to minimize scale formation. The process also requires a lot of electricity to operate

the vapor compressor, about 18 to 35 kWh per metric ton of water evaporated. To
minimize the size and cost of the vapor separator and compressor, evaporation

occurs at atmospheric pressure. The process flow diagram and a photo of the

system are shown. Source: HPD LLC

The wastewater flows to the evaporator feed tank, where acid is added to neutralize
bicarbonate alkalinity so that the solution can be preheated in plate heat exchangers.
Proprietary antiscalant formulations are usually added to avoid scaling in the preheaters
with calcium carbonate. The preheated purge stream is then deaerated using steam
from the evaporator (the red line in Figure 1) to drive off dissolved carbon dioxide from
the alkalinity reduction, dissolved oxygen, and any other non-condensable gases (the
red vertical vent). Venting these gases reduces the potential for corrosion of the
evaporator vessel.

Most of the water evaporation occurs in a falling film evaporator (inside the brine
concentrator vessel) that is seeded with calcium sulfate to minimize scale formation.
Wet FGD wastewater is typically saturated with calcium sulfate, which will tend to
precipitate and form scale on the evaporator tubes. When calcium sulfate seed crystals
are present, the dissolved calcium sulfate precipitates preferentially on the seed crystals
rather than the evaporator tubes.

The process also requires electricity to drive a mechanical vapor compression (MVC)
cycle. Because MVC recycles the latent heat of vaporization, the energy input is quite
low—in the range of 18 to 35 kWh per metric ton of water evaporated. To minimize the
size and cost of the vapor separator and compressor, evaporation occurs at
atmospheric pressure.

The Cost of Crystallizing

The falling film evaporator will concentrate wastewater, but it will not crystallize large
quantities of dissolved salts. Crystallization occurs in the forced-circulation evaporator-
crystallizer, an evaporator design especially suited to the propagation and growth of
crystals within the bulk solution (Figure 2). The evaporator/crystallizer is integrated with
a solids-dewatering device (such as a centrifuge or pressure filter), which separates the
salt crystals from the product slurry. The mother liquor is returned to the crystallizer for
further concentration.
2. Crystallizer process. The falling film evaporator will concentrate wastewater but

will not crystallize large quantities of dissolved salts, so additional processing is

required. A crystallization of the solids occurs in the forced-circulation evaporator-

crystallizer. The remaining solids-heavy waste stream is then sent to a solids

dewatering system to remove any remaining water. The process flow diagram and a

photo of the system are shown. Source: HPD LLC

The forced-circulation evaporator is usually driven by an external source of steam. The

steam heating is required because of the high boiling point rise (BPR) of the solution at
the high concentration when crystallization of the dissolved salts takes place. The
crystallizer requires slightly more than a metric ton of steam to evaporate a metric ton of
water.

For most wastewaters containing 1% to 5% dissolved solids by weight, it is relatively

easy to remove 75% to 95% of the water in a falling film evaporator. When highly
soluble salts are present in the wastewater, the last 5% to 25% of water may be difficult
to evaporate and require further processing, as discussed in the following section. As
water is evaporated from a solution, the concentration and ionic strength of the salts
increase, as does the boiling temperature of the solution. The increase in boiling
temperature of a solution above that of water at a given pressure is called the BPR. The
BPR increases as the concentration of dissolved salts increases when evaporating
water from a solution.

Calcium chloride is the main dissolved salt in wet limestone FGD blowdown. As the
concentration of calcium chloride increases in the solution, so does the boiling point
temperature (Figure 3). The two curves intersect at the solubility limit of calcium chloride
in a boiling solution. Figure 3 also shows that calcium chloride is very soluble in water;
as a solution is concentrated by evaporation at 1 atmosphere (atm), its boiling point
continues to rise, until the solubility limit of about 75% by weight is reached and calcium
chloride dihydrate (CaCl2 • 2H2O) crystallizes out from solution. Figure 3 further shows
that a saturated solution of calcium chloride at a pressure of 1 atm has a boiling
temperature of almost 350F, a BPR of 138F.
3. Depressed boiling point. This figure illustrates the relationship of the boiling

temperature for pure calcium chloride solution against its solubility curve at

atmospheric pressure. As the weight percentage of the calcium chloride increases in

solution, the boiling point of the solution rises. This fundamental property of salt

solutions is an important design parameter. Source: HPD LLC

At this high temperature, calcium chloride, like magnesium chloride and ammonium
chloride, undergoes hydrolysis in water; that is, it releases hydrochloric acid that will
aggressively attack steel. The rate of hydrolysis increases with the temperature, so
materials of construction for the evaporator vessels and heat transfer surface must be
carefully selected to resist the extremely corrosive nature of these salts at high
concentrations and temperatures. Experience shows that suitable corrosion-resistant
materials at these temperatures and concentrations are very expensive noble alloys,
such as palladium-alloyed titanium and high nickel-chrome-molybdenum alloys. The
requirement for such expensive materials makes the use of a final crystallizer
economically challenging in most wastewater ZLD applications.

A Lower-Cost Approach

On projects where the use of a crystallizer is not economically feasible, a falling film
evaporator will recover 75% to 95% of the water and concentrate the wastewater that
can then be sent to an evaporation pond. If your project requires a full ZLD system,
there are several options to consider when exploring ways to handle the remaining 5%
to 25% of the original volume of wastewater (produced by the system shown in Figure
1). For example, it may be possible and economically attractive to construct a surface
impoundment to store the concentrate and let nature handle the evaporation.

Another alternative is spray drying to remove the remaining moisture from the
concentrate that produces a dry product suitable for landfill disposal. A spray dryer does
burn fuel oil or natural gas and will probably require an air emissions permit.

Other methods of drying the evaporator concentrate include flakers, prilling towers, and
other methods common to industrial salt production. The common drawback to drying
technologies is that they are quite energy-intensive (as high as 1,500 kWh per metric
ton of water removed) for the small amount of water evaporated.

For wet FGD wastewater where calcium and magnesium chloride salts predominate, a
pretreatment process may be preferable. Chemical softening using lime (calcium
hydroxide) and soda ash (sodium carbonate) can be used to remove most of the
magnesium and calcium ions in the wastewater as precipitates of magnesium hydroxide
and calcium carbonate (Figure 4). These precipitates settle in a clarifier, and the
resulting sludge is dewatered and then disposed of in a landfill. The net result of the
softening process is that sodium ions are substituted for most of the calcium and
magnesium ions, so the softened stream becomes mainly an aqueous solution of
sodium chloride.

4. Lime-soda ash-softening process. In wet FGD wastewater, for example, where

calcium and magnesium chloride salts predominate, chemical softening using lime

(calcium hydroxide) and soda ash (sodium carbonate) can be used to remove most

of the magnesium and calcium ions before the wastewater enters the evaporation

process shown in Figure 1. Source: HPD LLC

The softened stream is next evaporated in a falling film evaporator and water is
recovered, as discussed earlier. The final concentration step is using a forced-
circulation evaporator-crystallizer, in which the sodium chloride crystallizes at a
relatively low temperature and concentration (its solubility is 28.3% by weight at its
boiling point of 227.6F at 1 atm). The solid sodium chloride produced is mixed with the
softener sludge and is disposed of in a landfill.
The drawbacks to this scheme for ZLD are the cost of the additional equipment required
to soften the wastewater, the cost of chemicals and sludge disposal, and the additional
complexity of the overall process. On the other side of the ledger, this process allows
the use of less-expensive alloys in major process equipment.

A New, Low-Temperature Approach

HPD has developed a new ZLD process employing the approach used in industrial
crystallization of very soluble chloride salts: Operate the evaporator at low pressure.
Lowering the operating pressure allows water from the waste stream to evaporate at
lower temperatures. The chemistry of wet FGD and IGCC wastewater favors the
formation of many hydrates and double salts that precipitate at lower concentrations as
the temperature of the solution is lowered. The BPR of solutions is usually less at lower
temperatures.

When the waste stream, consisting of highly soluble salt solutions, is concentrated at
low temperature, dissolved solids will precipitate and crystallize at relatively low
concentration. Using the phase diagram of pure calcium chloride solution (Figure 3), we
see that several hydrated salts can form from calcium chloride solution, depending on
the temperature. The concentration at which these hydrated salts form decreases with
the temperature. For example, calcium chloride dihydrate forms at 350F from a solution
having a concentration of 75% by weight calcium chloride, but at 115F, it will solidify
from a solution having a concentration of only 56%.

Low operating temperatures have many advantages. First, they reduce acid hydrolysis
at high chloride concentration, allowing less-noble alloys to be substituted for the high–
Ni-Cr-Mo alloy materials of construction usually required for a crystallizer train
processing highly soluble chloride brines. The low process temperature also eliminates
the need to pretreat the feed brine to the ZLD process. Eliminating pretreatment avoids
solids settling and filtration equipment, sludge dewatering equipment, and chemical
feed/storage facilities, substantially reducing the footprint of the overall water treatment
facility. It also avoids producing a sludge waste product that is expensive to dewater
and dispose in a landfill.

By operating under vacuum, the boiling temperature of the solution is reduced from that
at atmospheric pressure, and a solid can be obtained at a relatively low concentration.
For example, the BPR is also lower when operating under vacuum at low temperature:
At 75% calcium chloride the BPR is 135F, but at 56%, the BPR is only 56F. Therefore, a
saturated solution of calcium chloride (58% by weight) will boil at 140F if the vapor
pressure is maintained around 0.5 psia, which is well within the capability of typical
industrial vacuum systems. The BPR of saturated calcium chloride solution at these
operating conditions is 60F. This means that the water vapor that evaporates from the
solution will be 60F less than the boiling temperature of the solution, or 80F.
A Simple Treatment System

HPD has used these low-temperature properties of very soluble salts found in plant
wastewater to design a unique low-temperature crystallization process known as the
CoLD Process (Crystallization of high-solubility salts at Low temperature and Deep
vacuum). This crystallization process is derived from methods used in the industrial
production of very soluble chloride salts.

The CoLD process is very simple, yet it is the only method that results in direct
crystallization of highly soluble salts, including chlorides, nitrates, and salts of organic
acids. The CoLD process combines a conventional vacuum-forced circulation
crystallizer with conventional heat pump technology to take advantage of the reduced
solubility and BPR of high-solubility salts at low temperature. Direct crystallization of
calcium chloride, magnesium chloride, ammonium chloride, or other high-solubility salts
using the CoLD process eliminates the need for extensive pretreatment of the
wastewater with lime, soda ash, and other chemicals to replace the calcium,
magnesium, and ammonium ions in the wastewater with sodium ions so that a
crystalline solid can be produced.

Figure 5 is a schematic of a CoLD crystallizer designed to operate at low temperature

and pressure. In this system, the heat required to boil the solution (it no longer requires
a separate source of steam) and the cooling necessary to condense the water vapor are
supplied by a closed-cycle heat pump. The refrigerating fluid is heated by compressing
it in the refrigerant compressor. Electrical energy, which drives the compressor motor,
provides the work that is the source of heat for the crystallizer. Part of the heat imparted
to the refrigerant by the compressor is transferred to the process solution in the
crystallizer heat exchanger by the condensation of the refrigerant.

5. CoLD crystallizer. HPD’s new crystallizer is designed to operate at low

temperature and pressure. The heat required to boil the solution and the cooling

necessary to condense the water vapor are supplied by a closed-cycle heat pump.

The process flow diagram and a photo of the system are shown Source: HPD LLC

The liquid refrigerant flows through an expansion valve into the condenser, where it
evaporates by heat transferred from condensing water vapor from the crystallizer. The
cycle is closed as the refrigerant flows back to the compressor. The energy input is
roughly 70 kWh per metric ton of water evaporated.

Besides a lower BPR, the lower operating temperature results in a much lower acid
hydrolysis rate for acid salts such as calcium chloride. The low-temperature operation
makes selection of the materials of construction easier when dealing with mixtures of
chloride salts, which are subject to hydrolysis. Low operating temperature translates into
a much less aggressive solution, so high-nickel or high–molybdenum alloy construction
materials are not required.

Laboratory testing has proven the effectiveness of this process on typical wastewaters
containing highly soluble salts. The solution depicted in Figure 6 is that of a typical
wastewater from a coal-fired power plant wet FGD system. After evaporation at low
temperature (131F), the wastewater was separated into high-quality distilled water and
a stable solid suitable for landfill.

 
 
Eliminating the need for water pretreatment avoids the need to install expensive solids-
settling and filtration equipment, sludge dewatering equipment, and chemical
feed/storage facilities—essentially, all the equipment shown in Figure 4. It also avoids
high chemical consumption and extensive sludge production and the resulting cost of
chemicals, dewatering, and landfill disposal. The CoLD process produces a solid
product consisting only of the solids originally contained in the wastewater plus a small
amount of acid required to eliminate the bicarbonate alkalinity in the equalized
wastewater.

The low operating temperature in the crystallizer reduces the need for high-alloy
materials of construction that are usually required for a crystallizer train processing high-
chloride brine. Direct crystallization of high-solubility salts using the CoLD process also
eliminates the need for inefficient and expensive drying equipment to produce a solid
product for disposal.

— William A. Shaw, PE (bill.shaw@ veoliawater.com) is a senior process engineer for

HPD LLC, a Veolia Water Solutions & Technologies company.