All Organic Program Pre-Section

Introduction:

The All Organic program is a non-heavy metal, non-inorganic phosphate containing program that operates
under alkaline conditions, generally in an alkaline pH range. It is designed for systems where the alkalinity and
calcium hardness will cycle up naturally to within the program guidelines. In some instances, acid may need to
be fed to maintain the proper pH and alkalinity range. The program works well in systems that are lower
temperature and have little halogen demand as high levels of oxidants will breakdown the organic
phosphonate portion of the program. These phosphonates are the main scale and corrosion inhibitors.

The All Organic program is useful in certain situations such as towers that are contaminated with NH3. The
program contains no heavy metals that can precipitate with sulfide such as zinc. Operation at high a pH allows
NH3 to naturally strip from the water in the cooling tower. The program does not contain inorganic
phosphate that will precipitate with soluble iron in the make up or tower water. The organic phosphates can
however, chelate the iron and therefore be inactivated. The highly buffered water chemistry is more resistant
to acid leaks or scrubbing of acidic gasses in a plant situation. This minimizes corrosion that can form in low
pH operation.

There are two basic programs in this family of products. One drum programs N-23265, N-23277(Eu), N-
23218(Eu), Phreeguard 2350 (aka N-55203), and N-8363 and either N-23267, N-23268, or N-23251. The N-
8363 is the active phosphonate version of the program while the three other products contain the polymer,
TT, TRASAR, and in some cases additional organic phosphate.

Corrosion Control:
The program provides corrosion protection by the formation of iron phosphonate, calcium phosphonate, and
CaCO3 films on the metal surface. Therefore, operation in the proper alkalinity range is imperative. The
other important factor is the ability to monitor and maintain the proper organic phosphate (phosphonate)
concentration in the system. While the CO3 may be an important factor for corrosion control, the
Phosphonates in the program control CaCO3 based scale as well as react with the metal surface to help with
corrosion protection.

The most common factors that affect the corrosion performance of the program are: water chemistry outside
the proper range and high halogen levels. High halogen levels will chemically degrade the phosphonates to
inorganic ortho phosphate. At the high operational pH of the All Organic program, CaPO4 scale will as the
phosphonates are broken down. This eliminates any corrosion inhibitor from the system.

The water chemistry factors are high conductivity, low calcium or alkalinity in the tower water. High
conductivity from Cl- and SO4 will affect the corrosion inhibiting film formation since the film is not as strong
as those developed in the A-Z Lite®, Stabilized Phosphate, or ASAP programs. The program generally works
well at conductivity of less than 3000 uS/cm in the tower. Low calcium or alkalinity levels will reduce the
driving force for the formation of the corrosion inhibiting film on the surface.
Scale Control:

Since the operation of the program is at high pH, the main scale that develops with this program is CaCO3.
The CaCO3 is controlled with the same phosphonates that provide corrosion protection. The phosphonates
are considered nucleation inhibitors as well as crystal modifiers, which means that as nucleation inhibitors
they prevent the earliest formation of scale crystal formation. As crystal modifiers, they distort the shape of
small preexisting scale particles preventing further growth.

High halogen levels that lead to the destruction of the organic phosphate result in CaCO3 and CaPO4 scale
formation. By far the primary scale formed is CaCO3. Operation outside the required Ca and alkalinity range
can also cause CaCO3 by overwhelming the phosphonates and causing uncontrolled deposition of Calcium-
Phosphonate complexes. The Prism polymer will help the dispersion of these complexes. But loss of over all
scale control is seen.

The program is given operational limits of 80-1000 ppm of Calcium and 300-500 ppm of alkalinity. The
program cannot operate at the upper end of both limits at the same time. When operating at calcium of >700
ppm the alkalinity needs to be minimized at 300 –325 ppm. When operating at low calcium levels (<100 ppm),
the alkalinity needs to be maximized and can be as high as 3000-4000 ppm.

All Organic Program Control Guidelines

Calcium
The maximum calcium level for the program is dependent upon the alkalinity and temperature of the tower.
The program operates over a relatively wide range of calcium from 80 to 1000 ppm as CaCO3. It is important
to realize that as the calcium in the tower increases, the alkalinity must decrease to ensure corrosion and scale
protection. For example, at 700-1000 ppm of calcium, the maximum alkalinity is only 325 ppm (or pH of ~8.3-
8.5) while at 80 calcium the maximum alkalinity is ~3000 ppm (or pH of > 9.0).

Alkalinity / pH
In general, the total or ‘M’ alkalinity in the tower is controlled between 300 – 500 ppm as CaCO3. Also of
importance is the ‘P’ alkalinity, at the maximum ‘M’ alkalinity of 500 ppm , no more than 30 ppm of ‘P’ should
be present to reduce the possibility of CaCO3 while at 300 the ‘P’ alkalinity can be as high as 90 ppm before
problems may be seen. In systems with very low calcium in the cycled up water (<100 ppm) the ‘M’ alkalinity
can increase dramatically to 3000 – 4000 ppm.

The pH of the tower can greatly impact the effectiveness of the program and the potential for either corrosion
or scale formation. The maximum pH is defined by the calcium concentration in the tower. As the calcium
goes to the program maximum (>700 ppm as CaCO3), both the alkalinity and the pH must be minimized to the
low end of the operational range. In all cases, the pH must be kept at or above 8.3 to allow ‘P’ alkalinity to
form for effective corrosion control. Below this pH, carbonate alkalinity does not form and corrosion will
become a problem on mild steel. At the low end of the calcium in the tower (<100 ppm as CaCO3) both the
pH and alkalinity must be maximized. The pH must above 9.0 in this case for the program to operate
effectively with respect to corrosion control.
Scale control is tied closely with these ranges. In general, if the pH of the tower water stays below 8.8 in the
calcium range of 200 – 600 ppm, scale control will be maximized. Above this pH range, proper product
monitoring and dosage control will help ensure minimal problems with scale formation.

Organic Phosphates
There are twotypical organic phosphates in the All Organic programs, HEDP and PBTC (AMP is in the N-23218
and N-55203 products). Each provides CaCO3 scale control as well as some mild steel corrosion inhibition.
The HEDP does the bulk of the mild steel corrosion inhibition. In general, the amount of phosphonate
required for corrosion inhibition increases in low calcium (<100 ppm) and in high calcium (600 ppm)
situations. The lowest requirements are with calcium levels between these two levels. At Calcium levels
above 600 ppm, the two drum program is preferred with the either N-23267 or N-23251 as the polymer
product because it includes additional PBTC phosphonate.

Inorganic Phosphates
The All Organic program cannot tolerate inorganic phosphate levels above 3 ppm in the recirculating water.
Higher levels will results in the formation if CaPO4 deposits. Since the program operates at a high pH, CaPO4
scale formation and deposition can occur rapidly. Be sure to measure the PO4 in the make up water and
calculate the theoretical PO4 at the operational cycles of concentration.

Silica
The rule of thumb limit on silica applies to the All Organic program. The limit of 150 ppm SiO2 should be
strictly adhered to. At this level of silica, any CaCO3 scale formation will likely cause SiO2 or MgSiO3 to co-
precipitate. In low hardness towers, local conditions may allow this limit to be exceed but no more than to
180 ppm SiO2.

Iron
Recirculating iron levels above three ppm will interfere with the normal operation of the All Organic program.
This is due to the reaction of the phsophonates with the iron. Reducing their effectiveness in corrosion and
scale control. Iron control strategies can help with additional polymer feed. The best method is to try and
remove the iron before it gets into the tower.

Aluminum
The All Organic program is not compatible with the aluminum in the water which can be carried over from
clarifiers. Levels as low as 0.5 – 1.0 ppm will cause the inactivation of up to 3 ppm Prism polymer and the
precipitation of Al- phosphonate complexes. Only increased dosages of product can overcome the effects.
The use of N-8344 has been found to be ineffective above a pH of 7.5.

Copper
High soluble copper levels are generally an indication of low azole levels in the tower water. Additional
product is likely to be needed to increase the azole to increase yellow metal corrosion protection. An
alternative is to feed a separate product containing azole such as N-1336 (concentrated TT), N-73199
(concentrated BZT) or N-73190 (Eu) -17% TT .

Holding Time Index (HTI)

The phosphonate HEDP will breakdown more rapidly to ortho phosphate than PBTC. This process is increased
with excessive chlorination and high iron levels. Application of the All Organic program in long HTI (>48 – 60
hrs) will see reduced effectiveness of the program. At long HTI’s the product feed will likely need to be
increased 25-50% to maintain effective levels of inhibitors in the system.

Temperature
The maximum temperature limit for the program is 135F (57C). This refers to the hottest water temperature
in the plant. At the maximum temperature, the program should be a two drum approach with additional
PBTC. This is needed to counter the increased corrosion and scale potential.

Chlorination
Good chlorination practices maintenance of a 0.2 – 0.5 ppm free residual. However, this level is harmful to
the HEDP phosphonate. It will also cause damage to cooling tower lumber increasing the delignification
process. Excessive chlorination will also cause degradation of tolyltriazole resulting in poor yellow metal
corrosion control. Consider the use of STABREX if it makes economic sense to you and your customer. This
stabilized halogen will reduce the degradation of the organic portions of the program. The use of N-73199 for
yellow metal protection should be considered since it is more resistant to degradation from halogens than is
TT.

Conductivity
The general maximum conductivity for the program is ~4500 uS/cm. This is dependent upon what ions lead to
the high conductivity. If it is due to high chloride and sulfate then a lower limit may be needed in the tower. If
it is due to carbonate in a soft water, high levels may be obtained. Generally, watching corrosion rates with
coupons is the best guide to setting maximum conductivity limits.

Products (These products may be out of date. Consult with the PAC-3 IDM or ITC.

Product HEDP Conc. PBTC Conc. Prism Polymer Azole TRASAR

Product Factor
N-23265 4.2% 6% 7.8% 1% (BZT) 100
N-8363 / 9% 12%
N-73231
N-23268 - - 10% 2.7% (TT) 75
N-23267 - 2.7% 10% 2.7% (TT) 75
N-23251 - 10% 9% 1.9% (TT) 200
N-7365/ 4.2% 6% 6.5% 2.5% (TT) -
N-2807T
N-23246 1.6% 2.3% 2.9% 0.7% (TT) 250
Phreeguard 4.5% 7.2% 2% NO Trasar but
2350/ N-55203 (AA/AMPS) 4.75% AMP
N23277 15% 15% 1% (BZT) 100
N-23218 4.2% 7% 8% 2% (TT) 100 (Product
Factor)
3.5% AMP
24% PR-1132
Monitoring and Control

The All Organic program is relatively easy to control with the use of TRASAR and the new actives polymer test.
Preferably testing for the phosphonate actives should also be done. Below are suggested tests that should be
performed on a routine basis to ensure control of the program and optimal results.

Test Frequency Program limits

Calcium 1/day 80-1000 ppm as CaCO3
‘M’ Alkalinity 1/day 300-500 ppm as CaCO3
‘P’ Alkalinity 1/day Typically 30 – 90 ppm as CaCO3
will vary per plant
Organic Phosphate 1/day 5-7 ppm as PO4 – may vary per
plant conditions
Polymer 1/day 5-7 ppm as Polymer – may vary
per plant conditions
Conductivity 1/day (Continuous w/controller) Typically 4000 uS/cm max. Can
vary per plant
Silica 1-2/week 150 ppm as SiO2 max
Iron 1-2/week 3 ppm as Fe , max
Ortho PO4 1/day 3 ppm as PO4 max
Free halogen 1/day 0.4 ppm

The limits may change per plant and per application. Let system results be your guideline for corrosion and
deposit results. The most critical factors for control are program actives (organic PO4 and Polymer) and free
halogen residuals.