UNDERSTANDING PHOSPHATE CHEMISTRY

Coordinated Phosphate Theory

Dissociation of phosphoric acid H3PO4=H+ + H2PO4- K1=7.5x10-3 (1) H2PO4- = H+ + HPO42- K2=6.2x10-8 (2) HPO42- = H+ + PO43- K3=4.8 x 10-13 (3) Consider the reaction PO43- + H2O = OH- + HPO42K3= 4.8 x 10-1 = [H+] [ PO43-]/[HPO42-] pH 12.318 = log (PO43-/HPO42-) Degree of hydrolysis of Na3PO4 to Na2HPO4 pH % complete < 9.0 100 9.0 100 10.0 100 11.0 95 12.0 67 13.0 17 14.0 2

Consider the reaction HPO42- + H2O = OH- + H2PO4pH- 7.218 = log[HPO42-/H2PO4-]

Degree of hydrolysis of dibasic phosphate to monobasic phosphate pH % Complete < 5.0 100 5.0 100 6.0 94 7.0 61 8.0 14 9.0 1 10.0 0.1 >10.0 0.0

Understanding Phosphate Chemistry I

Sodium phosphates are pH buffers. Disodium phophates arrests caustic soda. Na2HPO4 + NaOH = Na3PO4 + H2O Sodium to phosphate molar ratio (Na/PO4) Disodium phosphate is present if coordinate of PO4 & pH lies within the control boundary.
Orthopho sphates NaH2PO4 (MSP) Na2HPO4 (DSP) Na3PO4 (TSP) Na/PO4 1:1 pH of % solution 4.8

2:1

8.8

3:1

12.0

Understanding phosphate chemistry I..

Caustic is tied up in another form so that it cannot concentrate within the control boundary. Na:PO4 is used to describe mixtures of phosphates MIXTURE Na:PO4

TSP + DSP 2:1 to 3:1 65% TSP + 35% DSP 2.65 : 1 Equations to show boiler water chemical balance H3PO4 + H2O = HPO42- + 2H+ + H2O NaH2PO4 + H2O = HPO42- + H+ + Na+ + H2O Na2HPO4 + H2O = HPO42- + 2Na+ + H2O Na3PO4 + H2O = HPO42- + Na+ + OHNaOH + H2O = OH- + Na+ + H2O

Understanding phosphate chemistry II

The products of ionization of sodium phosphates are a function of pH CONTROLLING CAUSTIC pH increases with increasing Na:PO4 ratios (at equal PO concentrations). Solution pH and PO4 conc identify the form of phosphate Existence Na3PO4 Na2HPO4 Mixture of TSP & DSP TSP & caustic Na: PO4 ratio When the PO4-pH coordinate falls on 3:1 When the PO4-pH coordinate falls on 2:1 When the PO4-pH coordinate falls between 3:1 to 2:1 When the PO4-pH coordinate falls above 3:1

Understanding phosphate chemistry II .

The farther the PO4-pH coordinate is kept below the line 3:1, the greater the caustic absorbing capacity. What happens when free caustic is produced in the boiler? Na2HPO4 + H2O = (2Na+ + HPO42-) + H2O NaOH + H2O = (Na+ + OH-) + H2O (2Na+ + HPO42-) + (Na+ + OH-) = 3Na+ + HPO42- + OH3Na+ + HPO42- + OH- = Na3PO4 + H2O

Understanding phosphate chemistry III

What happens when excess caustic is present?
50 Na2HPO4 + 50Na3PO4 + NaOH = 49Na2HPO4 + 51Na3PO4 + H2O

(No excess caustic)

50 Na2HPO4 + 50 Na3PO4 + 51 NaOH = 100 Na3PO4 + NaOH + 50 H2O (Free caustic is present)

It is desirable to keep the Na: PO4 ratio between 2.1 to 2.8 during coordinate PO4-pH treatment. Na:PO4 ratio is to be determined only from the measurement of pH & PO4 in boiler water & not by the measurement of Na & PO4 The control charts are based on Na:PO4 of pur sodium phosphate solution. Other sources of Na in boiler water 1. Condenser leaks 2. Sodium sulphite in industrial boilers 3. Other impurities.

Understanding phosphate chemistry IV

As the boiler pressures & temperatures increased with a subsequent reduction in the design margin, caustic corrosion problems began to reappear. Tri Sodium phosphate has retrograde solubility. EFFECT OF SODIUM PHOSPHATE PRECIPITATION Solution Na:PO4 > ( 2.85 : 1) = (2.85 : 1) Between (2.13:1) to (2.85:1) = (2.13:1) < (2.13:1) Soild phase Na:PO4 Less than in solution Equal to solution Greater than solution Equal or greater than solution Greater than solution Effect Increases Na:PO4 of solution Solution Na:PO4 remains the same Decreases Na:PO4 of solution Solution Na:PO4 remains same Decreases Na:PO4 of solution

Variation of pH Vs PO4 with different ammonia levels in boiler water

Phosphate hide-out in high pressure boilers

Phosphate hide-out occurs in dirty boilers. PO4 conc decreases as the pressure is increased & PO4 conc increases as the pressure is decreased. MECHANISMS 1. Formation of Na/PO4 solids in occluded zones , such as under porous deposits or crevices. 2. Reaction of PO43- and Na+ forming iron oxides and their subsequent inclusion within the oxide layer. Fe3O4 + 3Na3PO4 +H2 + 2H2O = 3NaFePO4 + 6 NaOH Mechanism No:1 operates in a deposit laden & dirty boiler. Mechanism No:2 operates in units with magnetite during their formation such as immediately following an acid cleaning in which old magnetite layer is removed.

Phosphate hide-out in high pressure boilers Contd

Degree of phosphate hide-out during load changes is an indicator of unit cleanliness. A reduction in phosphate hide-out over a period of time is an indicator of the thickening or maturing of the magnetite layer and signal a need for chemical cleaning. Within the range of congruent phosphate control, phosphate hide-out does not upset the ratio of Na:PO4 in solution.

Congruent Control
It was found that the caustic attack continued to occur even when Na/PO4 mole ratio = 3.0 Presence of caustic due to precipitation of di-sodium phosphate at high temperature Congruent composition occurs at mole ratios of Na/PO4 2.85 at 300 deg C [ 86 kg/cm2 (g)] 2.65 at 365 deg C [ 197 kg/cm2(g)] Congruent composition: Composition of liquid & composition of solid phases are same. Congruent control offers very little protection against - silica volatalization - scale formation very susceptible to unexpected ingress of Na. PARAMETERS LIMITS Phosphate mg/L 24 Sodium hydroxide mg/L NIL pH 8.5- 9.3 Mole ratio Na:PO4 2.6 1 DSP mg/L 4 - 15

Neutral water treatment

In Russia, the NWT chemistry was implemented by use of gaseous O2. In Germany by using H2O2 Oxygen conc in feed water should be kept between 200 to 400 ppb REQUIREMENTS For NWT, feed water cation conductivity to be maintained between 0.15 to 0.30 micromho/cm pH of feed water between 6.5 to 7.5 Organics in condensate and DM water to be less than 0.37 ppm and 1.0 ppm respectively. No condenser leaks should be allowed. Copper alloy tubes should not be used in the feed water heaters and in the condensers.