Spotlight

Zero D
A Method of Reducing
Industrial Softener Discharge
By C.F. Chubb Michaud, CE, CWS-VI

ay the Green be with you! Now that Orange County

Californias Plant #21 has shown the world that sewage
can be converted back to potable water inventory,
every municipal wastewater treatment facility is looking to get
on the green wagon and do their share by recycling wastewater.
Reclaimed water in excess of 1,000 ppm TDS, however, has
limited value, and the pressure is on to reduce TDS creep by
limiting residential and industrial softener brine discharge. They
have your water softener in their cross hairs. Here is one way to
minimize your salt discharge while maintaining ultra-high brine
efficiency and capacity on your softening process.

Hard water limitations

Hard water, that which contains dissolved calcium and

magnesium salts, has issues with the industrial manufacturing
world. Hard water may interfere with manufacturing because:
It precipitates calcium and magnesium carbonate when
heated (as in a boiler).
It clouds and precipitates with an increase in pH (as in
chemical make-up).
It reacts with soap to form an insoluble scum (as in
dishwashers and laundries).
It precipitates when it concentrates (as in evaporative
coolers and ROs).
Calcium bicarbonate converts to carbonates when dried,
even at room temperature.
Soft water does none of these, which is why it is preferred
for industrial processes.

The salt issue (reaction 1)

When a softener exhausts and no longer can remove adequate

hardness ions, it is regenerated with a solution of sodium chloride
(salt). Generally, 300 percent of the stoichiometric amount of
salt is needed to produce the lower leakages required to satisfy
most commercial and industrial needs. In other words, softener
regeneration is about 33 percent efficient (residential units using
lower brine settings are about 50 percent efficient). So 33 percent of
the sodium in the sodium chloride goes onto the resin, displacing
calcium and magnesium, and 67 percent (along with 100 percent
of the chlorides) goes down the drain. A small industrial plant
operating 24/7 with a 50-gpm softener on 20-grain hard water
will discharge about 250,000 pounds of salt per year to drain.
That much salt will raise the TDS of 30 million gallons of distilled
water to >1,000 ppm TDS and make it nearly impossible to recycle
for agricultural and non-critical irrigation.
Water Conditioning & Purification

1. Softening
Ca(HCO3)2 + ONa+ OCa++ + 2 NaHCO3
Hardness + Resin
Resin + Soft water
2. Regeneration
OCa++ + NaCl ONa+ + CaCl2 + NaCl
Resin + Brine
Resin Waste + Excess brine
In addition, to regenerate the spent unit with soft water from
an alternating unit would result in an additional 1,380,000 gallons
of water down the drain every year (assuming 735.8 regenerations
per year at 75 gal./cu. ft. each time). Each run becomes 11.9 hours.
This represents five percent of the total system capacity.

Cost of operations

Sewer disposal
The 735.8 regenerations (assuming a 15 lb./cu. ft. salt dose)
per year will use (735.8 x 25 x 15) = 275,925 lbs. of salt at $0.06/
lb. = $16,555.
We consume 1,380K gallons of regeneration water @
$4.50/1,000 gallons = $6,210 for a total regeneration cost of
$22,765.
We produce a usable (50 x 60 x 24 x 365) = 26,280,000
gallons of process water. That works out to a regeneration cost
of ($22,765/26,280) $0.87/1,000 gallons.
Waste hauling
If this plant operated in an area with a zero-discharge limit
and all wastewater had to be hauled, additional expenses of
approximately $500 per 5,000-gallon tank truck and a disposal
cost of around $0.075/gallon would result. Each regeneration
cycle produces 1,875 gallons of waste (x 735.6 regens per year)
= 1,380,000 gallons = 276 tankers. Haul and dump costs are 276
x $500 = $138,000 plus disposal of 1,380,000 x $0.075 = $103,500
for an additional cost total of $241,500. The cost of soft water
increased by $241,500/26,280 or $9.19/1,000 gallons, increasing
the total to $10.06/1,000 gallons.
Brine reclaim
By initiating an aggressive recycling program, reclaiming
brine, backwash and rinse, the cost of salt, water and waste
disposal could be reduced. Using the reclaim scenario, the last 50
percent of the brine is captured and used as the first 50 percent
for the subsequent regeneration cycle. Lets look at some numbers
and work backwards. 7.5 lbs. of salt will offer a capacity of about
April 2010

22,500-gr./cu. ft. At the 15-lb. level, we see about 30,000-gr./cu.

ft. The last half of the brine only produces a capacity gain of 7,500
gr./cu. ft. Therefore, we are only using 7,500/6,000 (theoretical
value for amount of hardness removed per pound of salt at 100
percent efficiency) = 1.25 lbs. of that salt. The last half still contains
6.25 lbs. of NaCl. Process last half with virgin brine, for a total
dose of 13.75 lbs. This will divert the initial portion of the slow
rinse water back to the brine silo to replace the water portion of
the sweet brine used for make-up (approximately 75 gallons),
and a portion of the rinse goes to dilution of saturated brine to
make up the sweet brine (approximately 90 gal.). The backwash
water will be filtered and recycled. The fast rinse will find a home
Figure 1. Simplified brine reclaim schematic

within the plant (sewer may be an option here). Only the spent
brine and small portion of the slow rinse (at 25 gal./cu. ft. or 625
gallons per regeneration) will be disposed of (see Figure 1).
By reclaiming brine, a system will operate at 13.75 lbs./
cu. ft. and deliver about 28,500-gr./cu. ft. Based on a water
need of 26 mg/yr., the system has to be regenerated 738 times,
plus another (must allow for the capacity to produce fast rinse
volume of 20 gal./cu. ft. even though hauling isnt necessary)
25.9 times to produce water for regeneration. This results in the
need to haul the waste from 764 regenerations or 477,500 gal.
or 96 tankers/year. Haul-and-dump costs will run (96 x $500) =
$48,000 plus (477,500 x $0.075) = $35,813, a new total of $83,800/
yr., or $3.19/1,000 gallons of soft water produced.
In addition, salt usage was reduced to 143,250 lbs./
yr., saving $8,595 and cutting water for regeneration to
477,500 gal./yr. (saving 902,500 gallons) and $4,060. Total
savings of $12,655 reduce regeneration costs by $0.48/1,000
gallons (a new net of $0.40), resulting in a cost of softening
water to $0.40 (salt and water) + $3.19 (haul and disposal)
or $3.59/1,000 gallons.

A quest of impossibility

There is considerable effort being put forth at the moment to develop clever recycle schemes with minimal water
use and build the ultimate efficiency softener. Even ultrahigh efficient softening regeneration, however, still dumps
chlorides. Hardness that is stripped off the resin during regeneration goes down the drain as calcium and magnesium chloride. The
chloride issue has been the primary sticking point with California
and other restricted areas. High chloride is considered harmful
to both plant and animal life, and its presence reduces the ability
to reuse that water for agriculture or aquaculture. So no matter
how clever, no matter how efficient, no matter what, the brine
must be hauled off site at considerable cost.
Figure 2. Zero D schematic for in-plant regeneration

Water Conditioning & Purification

Total recycle approach

A 1994 article1 described a regenerant recycle and reclaim

system whereby the excess sodium and chlorides from the
regeneration are captured and retained in the plant, while the
hardness that is regenerated off the resin was precipitated. The
very reactions that cause hardness ions to drop out make this
system work. An excess of brine (either sodium or potassium)
can be used because theres almost 100-percent recovery of the
excess. For pilot plant runs done in 1994, a level of 30 pounds of
NaCl were selected and achieved average
capacities of 36,000 grains+ per cubic foot
of resin with a brine efficiency of over
5,600 grains per pound. An added bonus
was the <0.25-ppm of hardness leakage
from the process. The process was called
Zero D.
With the Zero D process, hardness is
precipitated from the waste brine with a
near stoichiometric quantity (calculation
of the exact quantities of reactants and
products in a chemical reaction) of sodium
hydroxide (NaOH). All divalent ions
that are insoluble as the hydroxide form
(including calcium, magnesium, iron plus heavy metals such
as copper, zinc and lead) drop out of solution and settle. The
supernatant liquid (the clear fluid above a sediment or precipitate)
containing excess NaCl and NaOH stays in solution and is nearly
hardness free. Precipitate is drawn off to a thickening tank or
clarifier (where additional salt and caustic are recovered), and
the supernatant is then neutralized with dilute hydrochloric
April 2010

acid (HCl) back to NaCl. The following reactions illustrate the

process:
1. Softening
Ca(HCO3)2 + ONa+ OCa++ + 2 NaHCO3
Hardness + Resin
Resin + Soft water
2. Regeneration
OCa++ + NaCl ONa+ + CaCl2 + NaCl
Resin + Brine
Resin
Waste + Excess brine
3. Precipitation
CaCl2 + NaCl + NaOH Ca(OH)2 + NaCl + NaOH
Hardness + Excess brine + Caustic Lime(ppt)
Reclaim
excess
4. Neutralization
NaCl + NaOH
Reclaim excess

+ HCl NaCl + H2O

Acid
Reclaimed brine

From theory to practice

For our example, we will assume that we have targeted

a 25-lb. salt/cu. ft. regeneration level and achieve a capacity
of 35,000-grains/cu. ft. With 25 cu. ft. of resin, each cycle will
remove 875,000 grains of hardness. With 20-gpg hardness, thats
43,750 gallons (14.6 hrs. at 50 gpm). We will filter and store our
backwash and slow rinse water for reuse.

precipitated lime will be drawn off and excess caustic neutralized

with 32 percent HCl (reaction #4). Due to addition of an extra 10
percent of NaOH, it will be neutralized with 9.0 lbs. of 100-percent
HCl (3.0 gallons)see reaction #5. By using 50-percent NaOH and
32-percent HCl, we are able to maintain our brine strength at 11
percent. The sludge continues to thicken and additional brine can
be drawn off to maintain the sodium levels (see Figure 2).
5. Salt make up
NaOH + HCl NaCl + HOH
Base + Acid
Salt + Water
In this example, we used 17.5 gallons of 50-percent NaOH
(111 lbs.), and 3.0 gallons of 32-percent HCl (9.0 lbs). At $650/
ton ($0.325/lb.) for chemical, the cost was approximately $39.00
per batch to produce 43,750 gallons of soft water and recycle
and reclaim 100 percent of the water used to regenerate. Some
water is lost with the sludge, resulting in a regeneration cost of
($39.00/43.75) = $0.89/1,000 gallons for chemical and $0.01 for
water. This cost ($0.90/1,000 gallons) is comparable to the cost of
salt regeneration and direct sewer discharge cited earlier.

Comparison of costs

Table 1 shows a comparison of costs in terms of 1,000 gallons

of soft water produced. This includes the cost of the water used
to regenerate, chemical and waste disposal costs (see Table 1).

Table 1. Comparison of costs

Using an 11-percent brine containing

Cost per 1,000 gallons
1.0 lb. NaCl/gal., we introduce 25 gallons of

Dosage
Capacity
Water
Chemical
Haul
Total
brine/cu. ft. or 625 gal./cycle. Initial effluent
Method
(lbs)
(gr)
($)
($)
($)
($)
from the regeneration will be water from the
Brine
and
dump
15
28,570
0.24
0.63

0.87
backwash, which is diverted to the backwash
tank. Once TDS starts to climb, we divert the
Brine and haul
15
28,570
0.24
0.63
9.19
10.06
next 730 gallons to a spent-brine storage tank
Brine recycle
7.5
28,500
0.08
0.32
3.19
3.59
and the slow rinse is diverted in two aliquots
Zero
D
25
35,000
0.01
0.89

0.90
of 450 gallons each to two storage tanks.
Slow-rinse water will be recycled using the
Conclusions
higher TDS first and the cleaner portion will finish. As with the
It appears that considerable cost reduction could be derived
brine reclaim example, the fast rinse will be used for plant utility.
for a small industrial plant that has to haul brine waste from
It will be slightly elevated in TDS initially. Total fast rinse will
softener regeneration. Chemical precipitation and judicious water
be about 400 gallons. We now have about 12 hours to precipitate
recycling can reduce operating costs by perhaps 90 percent. In
and clarify reclaimed brine for the next cycle.
addition, the higher capacity derived from high brining can cut
the number of regenerations by up to 20 percent, with additional
Hardness in reclaimed brine
savings on manpower as well. Brine recycling can reduce costs
For the purpose of calculating costs, we will work on pure
by almost 65 percent, with very little additional equipment.
mathematics based on the theoretical reactions. 35,000-grains/
Recycling saves on salt, water and hauling costs.
cu. ft. is equal to a 1.62-gram equivalent of hardness per liter of
resin. Using 25 cu. ft. (28.32 liters of resin comprise a cubic foot),
Note
the total capacity of the system is (1.62 x 28.32 x 25) = 1,147 gram
After the first pilot study in 1994, I was able to find users
equivalents of hardness. Since this much hardness is removed
for the milk-of-lime sludge produced by this system. Lime and
from the resin with each cycle, and if it is assumed that we have
magnesium oxide are used for the precipitation of metals from
pure calcium hardness (equivalent weight = 20), 22,950 grams
plating-rinse recovery systems and other metal surface-finishing
(or 50.5 lbs.) of calcium per cycle will be removed. If that much
operations. This particular sludge is an average of 80-percent
calcium were to have precipitated as CaCO3 scale, it would
calcium and 20-percent magnesium oxide. It also contains some
amount to 126 lbs. Thats a lot of scale reduction.
sodium hydroxide, making it not only effective but highly
To precipitate that much calcium will take 1,147-gram
desirable (the buyer even offered to pick it up). The incidental
equivalents of sodium hydroxide (equivalent weight = 40)
content of heavy metals is passed along to the next individual
or 101 lbs. At 6.364 lbs., 100 percent per gallon of 50-percent
whos really into heavy-metals precipitation, and also takes the
NaOH, we need 15.9 gallons. This is the stoichiometric amount
hand-off on potential disposal problems. Each batch of 25 cu. ft.
to replace sodium that was actually used to push calcium off the
would produce approximately 141 lbs. of dry lime (CaO).
resin. We also have to add a driving force by raising the pH to
approximately 10. Since there is little alkalinity to buffer the salt
References
solution, 110 percent of stoichiometric will be used, giving a total
1. Michaud, C.F., Water SofteningYesterday, Today and Tomorrow,
NaOH addition of 17.5 gallons. After precipitation (reaction #3),
WC&P, August 2003.

Regeneration (reaction 2)

Water Conditioning & Purification

April 2010

2. Michaud, C.F., Zero Discharge Softener

Regeneration, WC&P, March 1994.
3. Michaud, C.F., Minimizing Waste Dischargethe Zero D Concept. 2009. Paper
presented at PWQA Annual Conference.

About the author

S C.F. Chubb Michaud, CE, CWS-VI, is CEO

and Technical Director
of Systematic Company,
which he founded in 1982.
He serves on the Pacific
Water Quality Associations Board of Directors
(since 2001) and chairs
its Technical Committee.
Michaud has also been a
member of the Water Quality Associations
Board and Board of Directors as well as past
Chair of the Commercial/Industrial Section. A
founding member of WC&Ps Technical Review Committee, he has authored or presented
over 100 technical publications and papers.
Michaud can be reached at Systematix, Inc.,
6902 Aragon Circle, Buena Park, CA 90620;
telephone (714) 522-5453 or via email, cmichaud@systematixUSA.com.

Water Conditioning & Purification

April 2010