Date: 9-Sep-15

To: David Drips, Kiwon Jeon, Heemun Jang

Subject: Partial Neutralization Historical Testwork Review
Copies To: Thomas Gamarano
From: Kyle Marte

Summary
To date the partial neutralization unit operation has consistently failed to raise the CuSX PLS to the
design value of pH 2.0. This underperformance has prompted a review of the historical testwork and
design criteria. This review has indicated that the historical testwork results have been incorrectly
calculated and that the partial neutralization design is incapable of performing as designed. Implications
and recommendations are discussed.

Introduction
Since plant start-up, the Partial Neutralization unit operation has been observed to perform well below
expectation with the design target of pH 2.0 rarely being achieved (refer Figure 1). This
underperformance has continued despite increased specific ore dosing rates due to lower than design
flow rates of CCD overflow combined with near design rates of fresh ore addition. Additionally, leach free
acid levels have been well within the design limit of 15 g/L (refer Figure 2).

2.2

1.8
CuSX PLS pH

1.6

1.4

1.2

1
1/Jan 1/Feb 4/Mar 4/Apr 5/May 5/Jun 6/Jul 6/Aug 6/Sep
Date (2015)

Figure 1: CuSX PLS pH profile

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 16

14
Leach Discharge  Free Acid (g/L)

12

10

0
1/May 1/Jun 2/Jul 2/Aug 2/Sep
Date (2015)

Figure 2: Leach discharge free acid profile

The underperformance of partial neutralization had led to multiple secondary effects:

 Reduced recovery in leach due to constraints on leach acid addition in order to limit leach
terminal free acid.
 Low pH in CuSX PLS resulting in reduced SX recovery.
 Operational upsets in CuSX due to high TSS in PLS caused by increased solids loading in the
partial neutralization clarifier in an attempt to improve neutralization by increasing solids addition
to partial neutralization.

All of these listed problems are exasperated due to a positive feedback loop that occurs when acidic
raffinate is returned the CCD circuit as parallel wash and (when the plant is operated without iron
removal) primary wash. An estimated 95% of the acid from parallel wash and 45% of acid from primary
wash reports back to CCD1 overflow.

These factors have prompted a review of the historical testwork and design criteria of partial
neutralization.

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Historical Testwork Review
The design criteria for partial neutralization are based on testing conducted in 2008. A series of
neutralization test work was conducted by FLSmidth personnel under the direction of Emmitt Process
Consulting and is summarized in the memo “Boleo-Letter report to Mike April 9-revised”. The test work
was conducted at SGS Lakefield in parallel with the “Seven Samples” test work program (SGS Report
11798-001, 11798-002) under the direction of a representative of Baja Mining. In this series of tests,
ground or crushed ore was used to neutralize CCD overflow from the SGS Lakefield leach test work. The
results from these tests, as presented in the memo, are reproduced in Table 1. No raw data was provided
in the memo.

Table 1: Partial neutralisation results from “Boleo-Letter report to Mike April 9-revised”

The results are presented in normalized units of kg ore / m3 CCD overflow and range between 10-80
kg/m3. The design criteria is 150 t/h ore and 3200 m3/h CCD overflow yielding a specific addition of 47
kg/m3. The design criterion appears to be somewhat conservative with 5 of the 6 tests falling below 32
kg/m3 ore addition. However further investigation is required.

The critical design consideration for partial neutralization is the ore’s ability to consume acid (i.e. kg acid /
t ore). An attempt has been made to quantify this number from the historical test work. To calculate the
ore acid consumption, one must first determine the free acid at the initial pH and end pH. In complex
leach solutions, with varying levels of total sulphate and chloride, this is not a trivial exercise. Fortunately,
the differential free acid was determined during test 3 of the historical test work where the CCD overflow
pH was adjusted down from pH 2.0 to pH 1.7 with the addition of 8 g/L sulphuric acid. Note that this test
work was conducted when the flow sheet employed direct neutralization of leach discharge slurry – hence
the high initial pH. Similarly, test 4 shows 4.2 g/L acid required to acidify from 1.86 down to 1.70. Thus the
acid consumed by ore has been estimated to be 8.0 g/L for pH 1.72.0 and 3.8 g/L for pH 1.862.0.
From these figures, acid consumption can be back calculated and is presented in Table 2. It is noted that

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the pH range for most tests is greater than the pH 1.72.0 used to calculate the free acid resulting in a
slight underestimation of acid consumption.

Test #  1  2  3  4  5  6 
2006 dry  2004  TR 28  TR 125 Texcoco  TR033 
100  wet 100  whole  whole  whole  dry ‐ 
Ore Source  mesh  mesh  ore  ore  ore  28m. 
Initial pH  1.55  1.85  1.70  1.70  1.67  1.70 
End pH  1.97  2.01  2.2  2.15  2.09  2.05 
Estimated Acid Consumed (g/L)  8.0  3.8  8.0  8.0  8.0  8.0 
Ore Addition (kg/m3)  31.4  10  28.8  19.9  12.5  80 
Acid Consumption (kg/t)  255  380  278  402  640  100 
Table 2: Calculated acid consumption

These acid consumption figures are entirely nonsensical. To illustrate this, compare the partial
neutralization acid consumption to the oxidative leach acid addition, measured for the same ore samples
during the parallel SGS leach test work, in Table 3. Despite leach conditions that are exceedingly more
aggressive in oxidative leach (3 hour residence time at terminal pH 1.7 and 80°C) compared to partial
neutralization (20 minute residence time at terminal pH > 2.0 and 40°C), the partial neutralization acid
consumption is significantly higher. This is simply not possible! The acid consumption for Texcoco ore
at 640 kg/t is particularly outrageous. Boleo Coquina (carbonate/limestone) acid consumption is expected
to average only 550 kg/t. Note that the oxidative leach acid addition is the measure of concentrated acid
addition and does not account for acid from raffinate addition or from acid reporting as terminal free acid.
Though for the purpose of this analysis these two effects will very roughly cancel out and acid addition
can be directly compared to acid consumption.

TR 28  TR 125  Texcoco 

Ore Source  whole ore  whole ore  whole ore 
Acid Consumption ‐ Part. Neut. (kg/t)  278  402  640 
Acid Addition – Oxidative Leach (kg/t)  139  279  52 
Table 3: Comparing acid consumption/addition in oxidation leach and partial neutralization

Due to the surprising nature of these results, every attempt was made to verify all assumption and
calculations. As can be seen in Figure 2, the calculation for acid consumption is exceedingly simple and
the only unknown is the amount of acid neutralized between pH 1.7 and 2.0-2.2. For the whole ore tests,
8 g/L acid consumption based on the test work notes. This figure is based on the TR 28 whole ore test
and may differ for the others test which could have differing levels of total sulphate. This differential free
acid between pH 1.72.0 was also calculated using the from the SGS leach test work where the
reductive leach discharge (~ pH 1.7) was neutralized with Boleo Coquina (a.k.a. LBL = El Boleo
Limestone) to pH 2.0. Based on the stated coquina consumption, for each ore type, the acid neutralized is
estimated at ~4-5 g/L. While this is an appreciable decrease compared to 8 g/L, it still does not reduce the
calculated partial neutralization acid consumption to a sensible value.

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  g acid 
Acid Neutralised pH 1.7  2.0  
 kg acid 
Acid consumption    L sol' n    1000 L sol' n    kg acid    1000 kg ore 
      
 t ore   kg ore   m sol' n   1000 g acid  
3
t ore 
Ore usage  3 
 m sol' n 

Figure 2: Acid consumption calculation

A further verification is provided by reviewing the SGS scrubbing tests where acidic raffinate is slurried
with fresh ore. Tests done at 40% and 50% solids density with wet Texcoco ore and acidic raffinate were
conducted and resulted in a terminal pH of 1.58 and 1.98 respectively. The Texcoco sample stands out
for its low pH as the TR-028 and TR-125 samples were both neutralized above pH 2.5 (where metal
precipitation starts to occur and obscures any attempt to rationalize acid consumption). The acidity of the
raffinate was not measured but by taking a conservatory high estimate of 20 g/L the estimated ore acid
consumption is only ~10 kg/t. Again the partial neutralization test work results appear questionable.

In July 2008, as part of a testwork program on iron removal, an additional partial neutralization test was
conducted by Emmitt Process Consulting at FLSmidth’s laboratories in Salt Lake City. These results
indicated that 91 and 62 kg ore / m3 CCD overflow were required to neutralize from 10 g/L free acid to pH
of 2.2 and 1.94 respectively. Assuming 2.0 g/L terminal free acid in the pH 1.94 case yields an acid
consumption of 129 kg/t. The ore employed was from the 2006 pilot plant which had a leach acid addition
(both oxidative and reductive) of 222 kg/t when run at pH 1.7. Based on this, the partial neutralization acid
consumption of 129 kg/t is plausible if the ore is relatively reactive. Unfortunately these results appear to
have been discounted as an outlier and were not considered in the circuit design.

Based on the above analysis, there is strong evidence to support the theory that the specific ore addition
figures (kg ore / m3 solution) have been misreported and could potentially be understated by up to an
order or magnitude.

Recommendations
With the design basis for partial neutralization based upon dubious test work, it is essential that new
partial neutralization test work be conducted with plant samples to determine the acid neutralizing
capabilities of partial neutralization. Once the expected pH rise in partial neutralization, based on
maximum ore addition, has been quantified the benefits and drawbacks of a less efficient partial
neutralization must be assessed. The benefits will be measured solely in increased recovery in CuSX
while the drawbacks includes increased risk of flocculant and/or suspended solids transfer to CuSX and
increased levels of calcium supersaturation in the PLS. This tradeoff will directly impact the decision to
proceed with the modifications to the partial neutralization circuit whereby the partial neutralization
clarifier will run with increased ore addition and reduced emphasis on clarity while CCD2 is decoupled
from the CCD circuit and will function as a PLS clarifier.

If the performance of partial neutralization proves sufficiently poor, consideration should be given to direct
neutralization of leach discharge with Boleo coquina. Leach tank 8 would be converted to a neutralization
tank by addition of coquina slurry. However coquina could only be added if there is excess available
milling capacity in the limestone milling circuit as this would create a demand that was not previously
considered. Dissolution of calcium carbonate in leach tank 8 would result in a rapid supersaturation of
calcium in the leach solution which may exasperate gypsum issues. The residence time in the
downstream slurry operations (Area 18) may be insufficient to significantly reduce supersaturation.

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The implications of underperforming partial neutralization will extent to determine a new leach terminal
acidity that balances the benefits of increased leach recovery versus decreased SX recovery.

Appendices
1. Untitled Memo “Boleo-Letter report to Mike April 9-revised (2)”
2. Seven Samples Program on El Boleo Ore samples, Project 11798-001 – Report, 2008
3. The Washability Characteristics of Samples from the Boleo Deposit, Project 11798-002 – Report 1
4. Test Program and F.L. Smidth Minerals, Salt Lake City, Raffinate Iron Removal Test Results, “Boleo
Report-July 08”

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