To : Shane Barker

From: Jomar Antuerpia

Date: September 13, 2017
Re: Scaling Occurrence Report

1) Discussion:
The formation of scale on select unit processes such is that in the elution and that in the CIL residue
transfer contributes to loss in total productivity of the plant. There are already instances of de-
clogging activities for scales on some of the equipment; heat exchangers, and CIL tails transfer pump
and pipe.
The areas mentioned are observed to be prone to scaling for the following reasons.
Elution- High temperature and high alkaline environment with solution contact to a non-uniform
surface.
CIL- High alkaline environment with susceptibility to supersaturation and slurry’s exposure to
hydrodynamic shear force. As such, the main driving forces for scaling in the plant can be determined
as accelerated kinetics, presence of numerous crystallization zones, and supersaturation.

a) Accelerated Kinetics
Higher temperature pushes CaCO3 (the most common form of scale) formation while high alkaline
conditions reduces its solubility. Temperature shocks, intense mechanical and hydrodynamic shear
forces, and sudden changes in pressure can all accelerate the kinetics of scale formation. These factors
are present in the plant as follows:
Elution CIL
High operating temperature and pressure as High pH,
required by the Zadra Process, Hydrodynamic shear forces present along the
Temperature shock present in the heat CIL residue line
exchangers
Pressure drop for solutions coming from
Elution column to heat exchangers.
Table 1: Conditions that promotes accelerated scale formation kinetics

b) Numerous Crystallization Zones

The non-uniform surfaces found on heat exchanger tubes, transfer pipes, and heat exchanger plates
promote the attachment of inorganic microcrystals and the build-up of adherent scale layers. Also
favorable nucleation sites are the dents, scratches, and/or protrusions where the solution/slurry flows.
Microcrystals continue to grow by means of adsorption as seen in Figure 1. Thus, nucleation sites
attached to a surface will push scale deposition rate forward as long as sufficient ions remain in
contact with it. Scale deposits are mostly a combination of hardened compounds that agglomerate
along with the initial species that already formed.

c) Supersaturation
Supersaturation occurs when dissolved cations and anions, such as Ca+2 and CO3-2 increase in
concentration to levels that exceed their normal solubility limits. It is most likely the case in the CIL
where lime is used to moderate the pH. Note that the solubility of CaCO3 decreases sharply at pH
greater than 9 (Figure 2). Furthermore, the current water hardness reading in the plant is already at
>1000 ppm which is in itself already very hard (see Table 2 and 4). Couple this with the mineral slurry
fed in the CIL increases the amount of species that can form scales in the system.
2) Conclusion
Based on the abovementioned conditions and the prominence of the said driving forces, the
formation of scales in the plant can be deemed inevitable.
Other places that will likely form scales are the piping in the CIL and Elution area, screens, choke points,
and CIL residue cyclone.

3) Recommendation:
Following are steps that can be taken to minimize the impact of scaling in the plant.
a) Schedule de-scaling activities
i) Elution
Current practice for the heat exchanger unit is by descaling via flushing with sulphamic acid.
A regular flushing should be scheduled to minimize the extent of scaling on the equipment
and be done as a preventive measure instead of a remedial action.
As per Sir Eden Taray, it was originally proposed to circulate sulphamic acid in the heat
exchangers after every five batches. Accordingly, it shall be implemented after elution batch
195. This initial 5-batch cycle should be investigated to optimize the usage of the acid.
ii) CIL
For the CIL residue cyclone feed pipe, de-clogging every two months can be primarily
employed. This is grounded on the historical account of stoppages related to de-clogging
activities (Table 5). Extent of scaling must be monitored every session to adjust the cycle time.
Note that the lesser nucleation sites are present the slower the deposition will occur. Thus,
thorough removal of scaling inside the pipe may decrease the preventive maintenance cycle
to more than a two-month basis.
Adding a secondary pipeline as spare can remove the downtime altogether as the cleaning
can be done to the alternate line while the other is in use.

b) Addition of scale inhibitor

i) Selection of a viable scale inhibitor that can be used in the system. Further scale analysis
should be done to determine the actual type of scale formed per area so that a much suited
reagent can be used. Primary suspected species are Calcium Carbonate and Calcium Sulfate.
 Common scale forming compounds in order of occurrence (Lloyd, 2015)
1. Calcium Carbonate
2. Calcium Sulfate
3. Silica Complexes
4. Barium Sulfate
5. Strontium Sulfate
c) Monitoring RSI water hardness
i) Source of scale forming ions and compounds are present in the return water used in the plant.
An increase in hardness can be observed starting July this year (Figure 3). Expected increase
in scaling can be drawn up from this observation. This increase in water hardness should be
further investigated and/or reduced to prevent other adverse effect on the plant.

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 d) Observe parameters strictly
i) Supersaturation is one of the driving forces for scale formation. In the plant, the source of
supersaturation of the slurry is the lime addition. Keeping tabs on the determined parameter
should be observed strictly to prevent further saturation of Ca+2 and avoidance of extremely
high pH where Calcium Carbonate solubility is greatly decreased.
ii) The potable water used for eluant mixing was determined soft (Table 3). Thus, it can be
eliminated as source of scales in the elution. The most likely source for the heat exchangers
are the inorganic materials that were carried over to the elution stage after the acid wash.
The extent of washing can not perfectly remove the unwanted species but increasing its
efficiency can prolong equipment condition. It is advisable to ensure the strength of the HCL
used.

4. Supporting Data
Calcium hardness
Date pH Conductivity (umho/cm)
(ppm)
September 4, 2017 1060 6.87 1477
September 5, 2017 1040 6.42 1458
September 6, 2017 1008 6.87 1557
September 7, 2017 1092 6.74 1594
September 8, 2017 1104 6.82 1572
Average 1060.8 6.744 1531.6
Table 2: RSI return water analysis c/o DYNA

RSI return water is the main source of water dilution in the plant. Based on the water system service
report submitted by DYNA Integrated Solutions, the RSI return water used in the plant has >1000 ppm
calcium hardness and >1100 ppm total hardness. This range of concentration which is way above 180 ppm
is considered very hard according to the water hardness standards.

Calcium Hardness
Date pH Conductivity (umho/cm)
(ppm)
September 8 2017 52 7.89 109.5
September 11 2017 56 7.64 109.5
Average 54 7.765 109.5
Table 3: Potable water analysis c/o DYNA

Potable water is used for the preparation of the eluant in the elution section. A test on its quality shows
that it is only slightly hard. A low conductivity can also be observed indicating that the levels of electrolytes
in it are low.

Degree of Hardness Grains per Gallon (gpg) ppm (or mg/L)

Slightly Hard 1.0-3.5 17.1-60
Moderately Hard 3.5-7.0 60-120
Hard 7.0-10.5 120-180
Very Hard >10.5 >180
Table 4: Water hardness standards

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 Date Activities Done
Dismantle the suction and discharge pipeline of CIL residue pump for de-
2017-8-25
clogging.
1) Open CIL residue pump due to scale on casing 2) Done; shifts
accomplishment - removed suction spool for operations team to de-clog
2017-8-2 hopper discharge port. 3) For monitoring; completed de-scaling inside of
pump casing, impeller and suction spool, but during running still low flow,
suspected clogged at the discharge line.
Descaling of CIL Residue pump (6200-PMP-07), suction and discharge
line. REMARKS: 1) Pulled out cyclone distributor 2) Carry out de-clogging
2017-7-2 by operations 3) Installed cyclone distributor 4) Re-installed suction and
discharge as per operations supervisor pipe opening is approximately
75mm
2017-5-7 De-clogging of CIL residue line
2017-3-4 De-clogging of CIL Residue Pump (12hrs Mill Shutdown)
2017-2-18 Clogged up CIL residue pump (6200-PMP-07).
2017-1-1 De-clogging of CIL residue pump
Table 5: Historical reports for maintenance activities relating to clogging and scaling on the CIL
residue pump and line

Record obtained from the MexData shows that there has been at least seven instances of de-scaling and
de-clogging activity for the CIL residue pump and pipe for the current year in an almost monthly basis.
There are however, no retrievable record for the de-scaling done in the heat exchangers in the elution.

Figure 1: Mechanism of Scale Formation

Figure 1 shows the mechanism of scale formation. With the right condition of concentration, pH, and
temperature, ion pairing will proceed and start the reaction chain. Growth from microcrystal to
macrocrystal increases exponentially as the intensity of attraction for aggregated compounds is directly
proportional to the mass of the microcrystals. Each microcrystals will function as a nucleation site if it

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doesn’t dissolve. The process of adsorption and accumulation affects not only the initial species but other
salts as well.

Figure 2: Solubility of Calcium Carbonate in pure water as function of pH

The figure above shows that at pH 10 and up, Calcium carbonate solubility closes to nil.

Figure 3: RSI return water calcium hardness report from Nov 2016 to present c/o DYNA

Graph shows a steep increase in total hardness of the RSI return water following the month of June to
July. Other than the recirculation of the minerals in the plant to the RSI and back, those that are carried
to the RSI when raining may have contributed to the observed increase.

4) References:

Lloyd, L. (2015). Presentation on theme: "Reverse Osmosis Feed Treatment, Biofouling, and
Membrane Cleaning"— Presentation transcript:. Retrieved from Slideplayer.com:
http://slideplayer.com/slide/6908559/

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 Y.Duggirala, P. (n.d.). Formation of Calcium Carbonate Scale and Control Strategies in Continuous
Digester. Napperville, Illinois, USA.

"PPO Maintenance work history" retrieved from:

http://172.32.16.11/MEXData/#/Assets/AssetRegister/97e9535d-49c8-4add-9ce7-ebe3b845458d

“CaCO3 Scale formation” retrieved from:

https://www.wqa.org/learn-about-water/perceptible-issues/scale-deposits