Improved Aluminum Leaching

R.A. Peterson R.L. Russell D.E. Rinehart

Outline
Historical leaching tests Development of leach factors Initial WTP process Revised process to achieve leach factors What we know today

Historical Leaching Tests

Between 1993 and 1998, approximately 32 separate leaching studies were performed on small samples 18 of those tests contained a large quantity of aluminum (greater than 100 mg/g) Typically process flow is shown on the next slide Most samples were leached for a total of 10 hours, however some boehmite samples were leached for up to 200 hours

Typical process flow for high Al samples

1 g of solids 0.8 g of NaOH (between 1 and 5 M) Leach 5 h at 100 C Decant leachate

1.6 g of NaOH (between 1 and 5 M)

Leach 5 h at 100 C

Decant leachate

Wash Sample

Impact of increasing NaOH on leaching performance

Contract target

Leach factor development (from Meacham - 2003)

Starts with waste type groups
36 waste types defined based on processing history

Leach factors were measured for 32 tanks Leach factor was estimated for 8 hours at 100 C in 3 M NaOH (usually an interpolation between 5 and 10 hours)
LF = 1 mf mi

Leach factor development

38 different waste groups
1C 1CFeCN 224 B BL BSltCk DE HS MW OWW3 P2IP3 PFeCN PL2 Portland Cement R-B R-NB RSltCk RSltCk-NB SISltCk-B SISltCk-NB S2SltSlr-SST S2SltSlr-DST SRR T1SltCk T2SltCk TBP TFeCN TH1 TH2 Z

2C BYSltCk AISltCk CWP A2SItSlr AR CWR CWZr

Leach factor development

Leach factors for each group are determined from weighted averages for the measured leach factors
LFk = LFTank p j LF j ( j k )
j =1 38

pk

Statistical analysis is used to regress data from all 32 tanks simultaneously Not all waste groups have been measured If a leach factor has been measured for a tank, that value is used If a leach factor has not been measured, the weighted leach factor from the regression is used

Leach factors for all 38 waste groups

B BYSltCk CWR CWP PFeCN DE S2SltSlr DST TBP IC P2IP3 1 1 1 0.961 0.928 0.87 0.746 0.739 0.7 0.588 MW OWW3 PL2 Portland Cement RNB TH2 Z TFeCN TH1 RSltCk 0.517 0.517 0.517 0.517 0.517 0.517 0.517 0.455 0.397 0.375 AISltCk RSltCkNB SISltCk NB S2SltSlr SST T1SltCk T2SltCk ICFeCN 2C SRR RB 0.374 0.374 0.374 0.374 0.374 0.374 0.372 0.346 0.329 0.236 HS 224 A2SItSlr AR BL BSltCk CWZr SISltCkB 0.178 0.131 0 0 0 0 0 0

Major Al sources highlighted in red Yellow highlights are estimates for groups that have not been tested

Initial WTP Process

1 g of solids Wash to reduce Na to < 1 M

Wash Water

1 g of NaOH at 3 M NaOH

Leach 8 h at 85 C

Wash Water

Wash to reduce Na to < 1 M

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Test Results 2000 to 2003

WasteSourceTank insolublesolids(g) NaOHadded(g) NaOH:insolublesolids(g:g) leachfactor leachateAl(M) leachateNa(M) C104 238 278 1.17 0.87 0.58 2.02 AZ102 118 144 1.22 0.47 0.37 2.35 AZ101 AY102/C106 328 282 0.86 0.73 0.54 2.63 9 2.4 0.27 0.7 0.58 4.90

Note: contract target was 0.62 g NaOH:g insoluble solids

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Leachates were slightly supersaturated relative to literature solubility limits

Literature solubility for pure hydroxide

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Process changes
Eliminated up front washing step Evaluated increasing leaching temperature to 100 C Initially reduced the caustic usage to contract target (0.62 g NaOH:g insoluble solids) Subsequently increased the caustic usage to avoid supersaturation

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Revised Process Flow

Sufficient NaOH to avoid supersaturation

5 wt% slurry

Dewater

20 wt% slurry

Leach at 100 C for 816 hours

Dewater/ Wash

Clarified supernate

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Test Conditions
Component Sodium Oxalate Gibbsite Boehmite Inert Solids (Fe) 19M NaOH (g) Condensate Supernate (g) Mass 6.5 22.73 22.73 12.99

Leached at 100 C Stirred with an overhead agitator at 140 rpm (full scale facility uses Pulse Jet Mixer Target was to dissolve ~50% of boehmite in 12 hours 1.54 g NaOH/g insoluble solids
200.27 274.96 259.82

Additional test ran without gibbsite 2.8 g NaOH/g insoluble solids

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Results

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Leachate composition

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Adjusting the caustic used to achieve target leach factor

Test ID Oxalate (g) Gibbsite (g) Boehmite (g) 1 6.5 23 23 2 5.2 18 18 10 3 3.9 14 14 7.8 4 2.6 9.1 9.1 5.2 Leached at 100 C Stirred with an overhead agitator at 140 rpm

Sludge Simulant 13 19M NaOH (g) Condensate (g) Supernate (g)

200 265 330 395 275 275 275 275 260 208 156 104

NaOH:Insoluble 1.54 2.55 4.24 7.60 Solids

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Results

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Leachate Composition

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Evaluating Decreasing Temperatures (using longer times)

TestID InitialWt% Solids PEPSimulant (g) CrOOHSlurry 19MNaOH DIwater(g) Temperature (C) NaOH:Insolube Solids 1 20 2 20 3 20 4 20
Stirred with an overhead agitator at 140 rpm Constant NaOH:Solids ratio

481.9 481.9 481.9 481.9 118.2 118.2 118.2 118.2 381.8 381.8 381.8 381.8 105.4 105.4 105.4 105.4 100 95 85 80

1.98

1.98

1.98

1.98

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Results

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Leachate Analysis

Decreasing T

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Caustic Leaching-Comparison to Lab-scale

0.9 0.8

0.7

0.6 A l in so lu tio n (M )

0.5

0.4

0.3

UFP-2 Leach - Caustic Added in PEP UFP-2 Leach Caustic Added in APEL PEP UFP-2

0.2

0.1

Preliminary unreviewed data

UFP-1 Leach - Caustic Added in PEP UFP-1 Leach - Caustic Added in APEL PEP UFP-1

0 0 5 10 15 Tim e 20 25 30

What we know today

The presence of gibbsite (or other Al bearing species) greatly suppress the dissolution of boehmite
The blending of gibbsite and boehmite will require the use of increased amounts of NaOH to achieve the same fraction of boehmite dissolution Decreasing the reaction temperature will require more NaOH to achieve the same fraction of boehmite dissolution (in the same amount of time)

The original target quantity of NaOH (0.62 g NaOH:g insoluble solids) was not sufficient to keep the Al concentration below the literature solubility limit
Very few tests have been performed at this low rate of caustic addition

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