REE bearing mineral recovery: a microflotation and surface

chemistrystudyusinghydroxamatecollectorsandcitricacid.

BrianR.Hart,StamanDimov&LiuyinXia
ResearchScientists:SurfaceScienceWestern,UniversityofWesternOntario,ResearchandTechnologyPark,
999CollipCircle,London,OntarioN6G0J3,Canada.

ABSTRACT
The recovery of rare earth elements (REE) is fast becoming of significant interest globally. Modern
researchanddevelopmentprograms(outsideChina)towardstheoptimizationofREEmineralrecovery
byflotationhavebeenlacking.Duetothemineralogicalnatureofmanyhostingdeposits,theseparation
and recovery flotation flowsheets can be very complex. As part of a research project, a selected suite of
hydroxamicacid collectors (Naphthoyl,Cyclohexyl,Benzoyl,Octyl,Tertabutylbenzoyl,Salicylic)were tested
inordertoexaminetheirpotentialforrecoveryandselectivity.Microflotationtestswereconductedona
feedsample,recoveryandgradeoftheproductswereusedtoevaluatetheirrelativeflotationefficiency
and selectivity and these results (flotation with the hydroxamate collectors) were compared to a
phosphoricacid/sulphonatecollectormix(shortenasmixed).Inthetesting,theflotationresponsewith
the hydroxamate collectors was significantly better than the mixed collectors on freshly ground (no
slimes removed) samples. Furthermore the tests revealed that for most of the hydroxamate reagents
tested, their dosage requirements to achieve recoveries at the same levels was less than that for the
mixedreagents.ProductassaysshowthatrecoveryofbothLaandCeissignificantlybetterforusing
thesalicylichydroxamateandthatNb,YandZrrecoveryarefavoredbyusingoctylhydroxamate.These
results indicate mineral flotation selectivity could be achieved by using selective hydroxamtes. Spectral
fingerprinting by TOFSIMS surface analysis has allowed for the identification of reagent species. TOF
SIMSsurfaceanalysesofgrainsanalysisconfirmedthatREEbearinggrainsreportingtotheconcentrates
are doing so in response to collector attachment whereas grains reporting to the tails are doing so in
responsetoalackofcollector.TheTOFSIMSsurfacedatabasbeenusedtoexaminethefactorspromoting
flotationstreampartitioning.

INTRODUCTION
TheThorlakedepositisaworldclassresourceofrareearthelements(REE)inCanada.ConcentrationofREE
from the host rocks will be accomplished by flotation. Detailed mineralogical analyses indicate that
bastnaesite (Ce, La)CO3F, allanite (Ce, Ca, Y)2(Al, Fe3+)3(SiO4)3(OH) monazite (Ce, La, Nd, Th)PO4 and
synchysiteCa(Y,Ce)(CO3)2Fcarrythemajorityofthelightrareearthelements(LREEs)whilefergusonite((Y,
HREE) NbO4) and zircon ((Y,HREE) ZrSiO4) carry the majority of the heavy rare earth elements (HREEs).
NiobiumandTantalumarealsohostedincolumbite(Mn,Fe2+)(Nb,Ta)2O6(Pauletal.,2009;Coxetal.,2010;
unpublishedAvalonreports).
Development work to optimize a REE mineral recovery process flowsheet is underway. The original
approachusedtoconcentratesREEmineralshasbeenflotationwithalkylphosphatesandphosphoricacid
esterasthecollectors.OpencircuitandlockedcycleflotationtestsalongwithpilotplanttestingontheThor
lakeorereportrecoveriesinthefollowingproportions:90%ofthezirconiumoxide,69%oftheniobiumoxide
and63%ofthetantalumoxide(Coxetal.,2010;S.ChehrehChelganietal.,2013).
ToimproveREErecovery,hydroxamates,asalternativecollectorsfortheThorlakeores,wereinvestigated.
Literature regarding the use of hydroxamates on REE containing mineral phases is indeed limited, with
much of it published in Chinese. Pradip and Fuerstenau, reporting on the flotation of bastnaesite from
Mountain Pass ore using both fatty acid and alkyl hydroxamate collectors concluded that n
octanohydroxamate(OHA)wasamoreselectiveflotationreagentthanthefattyacid(Pradip&Fuerstenau,
1983, Fuerstenau & Pradip, 1984, and Pradip & Fuerstenau, 1991). There have been several successful
investigations reported on the flotation separation of rare earth minerals in general, and bastnaesite in
particular,withhydroxamatecollectorssincethen(Pavez&Peres,1994;Pavezetal.,1996;Assisetal.,1996;
Fuerstenau, 2005, Lee et al., 2009; Cui et al., 2012; Pradip & Fuerstenau, 2013). The investigation of
hydroxamateflotationofREEmineralshasnotbeenlimitedtonoctanohydroxamateandXuetal.,2002,Ren
et al., 1997 and Cheng et al., 2007 reported the use of naphthalenic hydroxamate collectors in rare earth
flotation. Currently, naphthalenic hydroxamates are the most commonly used collectors for rare earth
mineralsinChinasREEflotationoperations(Zhaoetal.,2000;Chenetal.,2000;Liuetal.,2006andZhang&
Edwards,2012)withtheseplantsproducingmorethan2/3oftheworldscumulativerareearthproduction.
Subsequent to the flotation testing using alkyl phosphates and phosphoric acid ester as the collectors a
testing program was initiated by the metallurgical group at Avalon to evaluate the effectiveness of the
hydroxamatecollectorsLFP81(naphthalenichydroxamate)andBzH(Benzylhydroxamate).Aspartofthis
programaresearchprojectwasalsoinitiatedtoevaluatetherecoveryandselectivityperformanceoflarger
suite of hydroxamate collectors (Naphthoyl, Cyclohexyl, Benzoyl, Octyl, Tertabutyl benzoyl, Salicylic).
Microflotationtestswereperformedonsamplesfromahomogenizedcompositefeedsample,withthemass
recovery and product assay used to evaluate their relative flotation efficiency and selectivity. The results
from the microflotation testing were also compared to similar testes performed with a phosphoric
acid/sulphonatecollectormix.

During the project we took the opportunity to look at the surface chemistry of the grains reporting to the
concentrates and tails samples in order to identify surface chemical factors potentially influencing
concentrates or tail stream partitioning. The technique of choice for this analysis is TOFSIMS which is
describedindetailinSmartetal.(2007)andSmartetal.(2014).TheTOFSIMStechniqueissurfacesensitive,
capableofprovidingmonolayeranalysiswithpartspermillion(ppm)sensitivity.Arecentreviewregarding
variousmineralprocessingapplicationsofthetechniquecanbefoundinChehrehChalgani&Hart(2014).

METHODOLOGY
Mineralsandreagents
Themicroflotationtestfeedsamplewaspreparedinlabasfollows:asreceivedsample(2mm)wassieved,
thecoarsefraction(+200mesh,>75micron)wasprocessedinamildsteelballmill.Thesievedfinefraction(
200mesh,<75micron)andthemilldischargesample(200mesh,<75micron)werecombinedasstock.This
samplewasfurthercutto400mesh(<35micron)formicroflotation.Slimeswereseparatedfromthefeedore
bysettlingina100mlcolumnandremovaloftheupper30mlafter10minutes.
Microflotation
ThemicroflotationcellusedwasmodifiedfromSiweketal.1981).Theliquidvolumewas100mlandthe
charge sample size was 10 g. The cell was made of glass and was closed at the bottom by a glass frit of
nominalporesize<5m.Thepulpconditioningtemperaturewasmaintainedat25C,theimpellerrotation
speedwassetat2000rpmandbubblesweregeneratedbyacontrolledairflowat0.76ml/sat30psig.After3
minutes conditioning, the pulp pH was adjusted by NaOH to 8.59.0. Various modifying agents, collectors
and frothers (as required) were added later in sequence and the pulp was conditioned for a further 3 min
after each addition. The slurry was then transferred to the microflotation cell where separation was
performed for 5 minutes. A list of the various reagents used in the project is given in TABLE 1. For
comparison between reagents individual reagent testing protocols were optimized to achieve a target
recoverybetween12and15%byperformingmultipletests.Inallcasesthecomparisontestswereperformed
intriplicate;thedatashowninthegraphsisthatofthemeanofthetests.
Theconcentratesandtailswerecollectedandimmediatelyfrozeninordertopreservetheirsurfacechemical
characteristics. Aliquots of the float test products were analyzed by ICPMS in order to get the separation
efficiency. A separate sample was analysed by the TOFSIMS to identify the loading characteristics of
selected reagents on the surfaces of mineral grains reporting to the concentrates and tails. The analysis
providedacomprehensivesurveyofthesurfacespeciesonthemineralgrainsreportingtotheconcentrates
ortails.Theanalyticalapproachwasconductedtocomparestatisticallysignificantdifferencesinthesurface
composition of species particularly related to potential activation (or depression) of the examined mineral
phases.

Table1.Reagentsusedinmicroflotationtesting
Reagent

Name

Components

Collector

KBX36

Collector
Collector
Collector
Collector
Collector
Collector
Collector
Collector
Modifyingagent

LFP81
F1682&A845
H205
CHH
BzH
OtH
TBBZ
ScH
WaterGlass

Phosphoricacidester,Alkylsulfatesodium,Xyleresulphonate,
Alkylsuccinamate
naphthalenichydroxamate
Phosphoricacidester,Alkylsuccinamate
2hydroxyl3naphthoylhydroxamate
Cyclohexylhydroxamate
Benzylhydroxamate
Octylhydroxamate
Tetrabutylbenzylhydroxamate
Salicylichydroxamicacid
Na2O:SiO2(massratio2:3);3840%solution

RESULTSANDDISCUSSION.
ReagentComparisonSummary
Based on the chemical analyses of the minerals identified in the ore, elements La, Ce and Nd are
consideredrepresentativeofLREEmineralswhereasNb,YandZrareconsideredmorerepresentativeof
the HREE minerals; specifically columbite and zircon. This convention will be used throughout the
discussion.

Slime Feed
De-slimed Feed

OtH
OtH-S

60

60

40

OtH
OtH-S

50

Grade %

Recovery %

Mass Recovery %

80

10

70

100

40
30

20
2

20

10
0

OtH-Conc

OtH-Tails

La2O3 Ce2O3 Nb2O5 Nd2O3 Y2O3

ZrO2

La2O3 Ce2O3 Nb2O5 Nd2O3 Y2O3

ZrO2

Figure1.Massrecovery,REErecoveryandgradeformicroflotationtestswithandafterslimeremoval.Thesamples
labeledOTHSisthenondeslimed(asreceived)sample.

EffectofSlimes
Lock cycle and pilot plant flotation testing using KBX36 revealed the inclusion of slimes in process
resultedinpoorrecoveryandgrade(unpublishedAvalonreports).Thiswasconfirmedbymicroflotation
testing using KBX36 but after removal of the slimes the response improved considerably (data not

shown). Testing with the hydroxamate collectors revealed that there is statistically no difference in the
massrecoveryforsampleswithandwiththeslimeremoved.Analysesoftheflotationproductsshowed
thatthereisalmostnodifferenceintherecoveryandgradeofLREEswhereasthereisaconsistentslight
buthigherrecoveryandgradenumbersfortheHREEsforthesampleswithslimeincludedinthetests.
(Figure1).

10

Grade %

KBX 36
F1682+A845
TBBZ
CHH
ScH
OtH
BzH

La2O3

Ce2O3

Nb2O5

Nd2O3

Y2O3

ZrO2

Figure2.REEgradeofconcentratesfrommicroflotationwithdifferentreagents
70

60

KBX36
F1682+A845
TBBZ
CHH
ScH
OtH
BzH

Recovery %

50

40

30

20

10

La2O3

Ce2O3

Nb2O5

Nd2O3

Y2O3

ZrO2

Figure3.REErecoveryofconcentratesfrommicroflotationwithdifferentreagents

ThegradeandrecoveryresultsfromthemicroflotationtestsusingdifferentreagentsareshowninFigures
2and3andTABLE2(includesREEcontentofthefeed).FromthedatashowninFigure2,amongthefive
hydroxamates(CHH,TBBZ,ScH,OtHandBzH),theLaandCegradefortheconcentratesproducedby
ScHishighest,suggestingthatitmaybeselectiveformineralscarryinglightrareearths.TheNb,YandZr

gradeforconcentratecollectedfromthemicroflotationwithOtHandBzHissignificantlyhigherthanthat
forCHH,TBBZ,ScH,suggestingtheymayhaveaparticularaffinityforzirconandcolumbite;theaffinity
forzirconiscertainlyindicatedbytheveryhighconcentratesZrO2grade.Incomparison,theconcentrate
grades with the mixed collector KBX 36 aresimilar to that of ScH; good grades for La, Ceand Nd,less
effective for Nd, Y and Zr. Like ScH, the data suggest an affinity for LREE over HREE minerals. The
concentratesgradesusingthemixedcollectorF1682+A845donotappeartostandoutrelativetotheother
collectors;howeveritdoesappeartohaveapartialaffinityforzircon.
Table2.REEcontentinthefeed;gradeandrecoverydataformicroflotationconcentratesfromtests
performedwiththedifferentreagents.

Feed
KBX36
F1682+A845
TBBZ
CHH
ScH
OtH
BzH

KBX36
F1682+A845
TBBZ
CHH
ScH
OtH
BzH

Grade(%)
La2O3 Ce2O3
0.5700 1.2767
2.1649 4.8959
1.5692 3.4904
1.3159 2.9282
1.7310 3.8886
2.4394 5.3645
1.8788 4.1932
1.9280 4.2635

Recovery(%)
La2O3 Ce2O3
61.04
61.63
61.48
61.05
51.63
51.81
49.24
49.30
44.84
45.03
60.19
60.04
54.54
54.15

Nb2O5
0.9813
1.0071
1.2589
1.0042
1.0128
0.8183
1.5822
1.5450

Nb2O5
16.49
28.64
28.14
21.23
13.43
27.63
18.91

Nd2O3
0.6858
2.5893
1.6352
1.3506
1.7752
2.5193
2.0155
2.2884

Nd2O3
60.67
53.24
48.81
46.40
42.32
58.63
52.78

Y2O3
0.5333
0.7518
0.7797
0.6629
0.6807
0.5918
1.1023
1.0311

Y2O3
22.65
32.64
34.09
25.33
15.44
34.43
25.09

ZrO2
3.9308
4.3091
5.5518
5.1195
4.6873
3.6066
8.4290
7.2943

ZrO2
17.62
31.54
32.65
22.70
13.14
32.37
22.79

The results from the microflotation testing show that the recovery of LREE minerals ranges from 45 to
60%whereasfortheHREEstherecoveryisconsistentlylessthan30%(Figure3).Amongthehydroxamate
collectors, OtH is the most effective for the recovery of LREE minerals and both OtH and TBBZ are
effectiveandshowsimilarrecoverylevelsfortheHREEminerals.ForKBX36orF1682+A845therecovery
of La, Ce and Nd is similar to that for OtH whereas F1682 + A845 appears to be more effective for the
HREEs.ItshouldbepointedoutthatthisrecoverydataforKBX36orF1682+A845doesnotcalculatethe
proportionofslimeremovedwhichaccountsforapproximately15%ofthematerial.Afterrecalculation,
the mass recovery and REE grade results are diminished to levels similar to those for TBBZ, CHH and
ScH.
FromthedatashowninFigures2and3andTABLE3,amongthefivehydroxamates(CHH,TBBZ,ScH,
OtHandBzH),OtHexhibitsthebestrecoverytoreagentconsumptionratioforthisore.Amassrecovery

of 17.9% was achieved in the microflotation tests using OtH at 250g/t where as for ScH, showing the
poorestoverallrecovery,adoseashighas20003000g/twasrequiredtoachievethesamemassrecovery
(~18%).PreliminarytestinghasshownsignificantrecoveryforOtHatonly250g/thoweverifthedoseis
increasedto500or1000g/t,theconcentratemasspullincreasessignificantly.
Table3.Collectoranddoseusedinmicroflotationtesting.
Collector
KBX36

Doseg/t
400

Collector
ScH

F1682+A845 500+300 OtH

TBBZ
250
BzH
CHH

1200

Doseg/t
20003000
250
1000

FlotationandSurfaceChemistry
Surface chemical analysiswas performed on selected REEgrains from several flotation tests in order to
determine1.Ifvariouscollectorsand/ordepressantscanbeidentifiedonthesurfaceofboththeREEand
ganguemineralsand2.Toidentifysurfacechemicalfactorswhichmaybeinvolvedineitherpromotingor
inhibitingrecovery.Thelaterislinkedtoastudyinvestigatingtheeffectsofvariousconditioningreagents
intheimprovementofREErecovery;specificallycitricacidandPb(NO3)2(publicationscurrentlyinprep).

In order to identify various reagents used in the microflotation, a sample of each was deposited on a
silicon substrate and analysed by TOFSIMS to generate spectral fingerprints. Spectral positions of a
characteristicpeakforthecollectorsBzHandLFP81aregiveninFigure4.Thedominantpeakpositions
foreachreagentexaminedwereusedtoidentifytheirpresenceandassessvariationsinloadingbetween
differentgrainsineachofthesamplesinvestigated.Reagent,activatingordepressantspecieloadingcan
provideinformationregardingfactorscontrollingmineralpartitioning.Analysedgrainswereidentified
bythepresenceofanyoralloftheREEelements.Distinctionswerenotmadebetweendifferentmineral
species.Foreachsamplemorethan35grainswereidentifiedandanalysed.

Intensity

x104

BzH

1.2
0.8
0.4

Intensity

x103

LF-P81

6.0
4.0
2.0
114

116

118

mass / u

120

122

124

Figure4.TOFSIMSspectraofcollectorsBzHandLFP81.Thearrowsidentifypeakpositionsusedasmarkersforthe
identificationofcollectorspeciesonthesurfacesofgrains.

The TOFSIMS data for LFP81 (naphthalenic hydroxamate) and BzH (benzyl hydroxamate) on REE
minerals from microflotation tests reveal a clear discrimination; REE minerals are reporting to the
concentrates in response to collector attachment Figure 5. For all collectors examined, there was a
considerabledifferenceinsurfaceloadingbetweengrainsfromtheconcentratesandtailssamples.

0.0025

8e-5

CollectorBzH

Outlier
90th Percentile

7e-5

Normalized Intesnity

NormalizedIntensity
Normalized Intensity

0.0020

0.0015

0.0010

5e-5

4e-5

0.0005

75th Percentile
Mean
Median

6e-5

25th Percentile
10th Percentile

CollectorLFP81

3e-5

0.0000
Pb 0 g/t C

Pb 0 g/t T
ConTail

Concentrate

Tail

ConTail

Figure5.Boxplotsshowingrelativeintensitydifferences(surfaceloading)forcollectorsonthesurfaceofREE
mineralsfromamicroflotationtest.

The surface examination also revealed that the grains reporting to the concentrates show higher
proportionsofREEelementsandoveralllowerproportionsofgangueionssuchasAlandamuchlesser
degreeSi(Figure6).

3e4

Al

La

0.018

2e4

N orm alizedIntensity

N orm alizedIntensity

3e4

0.020

1e4

1e4

5e5

Outlier
90th Percentile

0.016

75th Percentile
Mean
Median

0.014

0.012

25th Percentile
10th Percentile

0.010

0.008

0.006
Con
Tail
ConTail
ConTail

Con
Tail
ConTail
ConTail

Figure6.Boxplotsshowingrelativeintensitydifferences(surfaceloading)forLaandAlonthesurfaceofREE
mineralsfromamicroflotationtest.

The data reveals a requirement for an increased proportion of RE elements present on the surface. The
higherproportionofAlandSionthemineralsinthetailscouldreflecteithertransferredspeciesorthe
analyses of a greater proportion gangue phases in the tail; Al and Si reflecting matrix components. The
resultsimplythatREEmineralflotationselectivityispromotedbycleanersurfacesandthattransferred
secondaryions(AlandSi)couldpotentiallyinhibitcollectorattachment.Thepresenceofattachedsurface
speciesandtheaffectsonthemineralshydrophobic/hydrophilicbalancehasbeendiscussedbynumerous
authors and the reader is referred to the recent publication by Smart et al. 2013 (and the numerous
referencestherein).

In an attempt to evaluate the flotation response with excess secondary ions in the pulp, microflotation
tests were performed to look at changes in recovery as a result of added Al ions and the subsequent
addition of citric acid. The flotation testing data reported here was performed with the collector F1682
(phosphoricacidester).Althoughhydroxamateswerenotusedinthesetests,giventheirstrongaffinity
forandstabilitywithtrivalentmetalions(Miller2005)webelievethattheflotationresponsewouldlikely
be very similar. The results from three microflotation tests (deionized water (DIW), DIW with the
additionof100mg/lAlandDIW+100mg/lAland500g/tcitricacid)revealthattheadditionofAlionsled
to an unexpected promotion of silicates to the concentrates and/or a decrease in REE mineral recovery,
decreasingtheREEgrade(Figure7).Theadditionofcitricacidrevealsareductioninthenegativeeffect
generatedbytheAlionsintheflotationwhichisshownbyanimprovementinREErecovery.

TOFSIMSsurfacechemicalevaluationofundifferentiatedgrainsrevealedthattheadditionofAlresulted
in a higher proportion of Al on the surface of grains reporting to the concentrate relative to the tails.
(Figure8).Aftercitricacidaddition,theintensitydiscriminationforAlbetweentheconcentratesandtails
is significantly widened as a result of grains reporting to the tails having less Al on their surface. This

increase in concentrates/tails intensity discrimination was also noted for the collector; it is significantly
higherontheconcentratesandslightlyloweronthetailsfromthecitricacidtestrelativetotheblanktest.
TheimplicationhereisthatsecondaryAlonmineralsurfacesishavingsomeimpactonflotationstream
partitioning.Howeverfromthedatawecurrentlyhave,itisnotentirelyclearastowhattheeffectis.

Effect of citric acid with Al ions

Blank (DI Water)

Blank (Al ions)
Citric acid (Al ions)

Grade/%

0
La2O3

Ce2O3

Nb2O5

ZrO2

Nd2O3

Y2O3

Figure7.Gradeoftheconcentratesfromthemicroflotationtestsconditionedwithdeionizedwater(DIW),DIWwith
additionof100mg/lAlandDIW+100mg/lAland500g/tcitricacid.

TheadditionofcitricacidimprovesREErecovery,presumablyinresponsetochelatingAlinsolutionand
potentiallyremovingitfromgrainsurfaces.PreliminarysurfaceevaluationofREEphasesaftercitricacid
additionhasshownhigherintensitiesofspecificREEsongrainsfromtheconcentratesrelativetothosein
theAladditiononlytest.Thisagreeswiththedatafromthepreliminarymicroflotationtests(Figure6);
thatREEmineralswithcleanersurfacesshowgreatercollectorloading.Thelackofchange(decrease)in
Alintensityonthesurfaceofthegrainsfromthecitricacidadditiontesthowever(Figure8)isnotwell
understood.ItmaybepartiallyrelatedtothefactthatgrainsforsurfaceanalysisintheAl/citricacidtests
were not differentiated with respect to matrix composition and, that the surface analysis from a
disproportionate number of gangue phases are biasing the analytical results in favour of the gangue
mineralsurfaceratherthantheREEminerals(moredetailsfromthisresearcharecurrentlyinpreparation
foraforthcomingarticlebyXiaetal).

0.040

0.0010

F1682-finger
print peak(1)
F1682fingerprintpeak(1)

Outlier
90th Percentile

0.0008

0.035

Normalized intensity

Normalized intensity
NormalizedIntensity

AlAl
Al

0.030

0.025

0.0006

75th Percentile
Mean
Median

0.0004

25th Percentile
10th Percentile

0.0002

0.020
0.0000

CA CitricAcid
0.015
Al-Conc
Al-Tails
Al,C-acid Conc Al,C-acid Tails
AlConAlTailAlCAConAlCATails

Al-Conc
Al-Tails
Al,C-acid Conc Al,C-acid Tails
AlConAlTailAlCAConAlCATails

Figure8.Boxplotsshowingrelativeintensitydifferences(surfaceloading)forAlandthecollectoronthesurfaceof
nondiscriminatedmineralsfromthemicroflotationtestswithAlandcitricacidadditions.

CONCLUSION
Microflotation testing was used to asses the recovery characteristics and selectivity of 5 different
hydroxamatecollectors.Basedonthemicroflotationtesting,thereappearstobesomedegreeofflotation
selectivity amongst the collectors investigated. ScH (salicylic hydroxamic acid) appears to be most
selectiveformineralscarryinglightrareearths(LRREs)whileOtH(Octylhydroxamate)andBzH(Benzyl
hydroxamate) may be selective for the HREEs; certainly showing a particular affinity for zircon and
columbite. The data also shows that among the five hydroxamates evaluated, OtH exhibits the best
recoverytoreagentconsumptionratiofortheoretested.

TOFSIMS surface analyses was used to determine if the hydroxamate collectors can be identified on
grainsandtoinvestigatepotentialsurfacechemicalfactorswhichmaybeinvolvedineitherpromotingor
inhibitingrecovery.Spectralanalysesofmicroflotationconcentratesandtailstestsamplesrevealedthatall
collectors could be identified on grains and that their measured intensities are significantly higher on
grains(bothREEandganguesilicatephases)reportingtotheconcentrates.Thedataalsosuggestedthat
selectivityandREEmineralflotationispromotedbyclean(freefromgangueionattachment)surfaces.
TheresultsfrommicroflotationtestswithaddedAlshowareductioninREEgradebypromotingsilicate
flotationand/orbyhamperingREEmineralrecovery.Citricacidadditionseemedtoreducethenegative
effectgeneratedbytheaddedAlionsandresultedinanimprovementinREErecovery.

ACKNOWLEDGEMENTS
TheauthorswouldliketothankAvalonRareMetalsforboththesupporttoperformtheseanalysesand
allowingustopublishthisinformation.AportionoftheresearchwasfundedbyaNSERCengagegrant
(EGP 42845611) to B. Hart. The National Nature Science Foundation of China (Grant No. 51004114is
gratefullyacknowledgedforprovidingsomemineralsamplesandreagents.

REFERENCES
Assis, S. M., Montenegro, L. C. M.,Peres, A.E.C., 1996. Utilisation of hydroxamates in minerals froth
flotation,MineralsEngineering,9(1),103114.
ChehrehChelgani,S.,Hart,B.,Xia,L.,2013.ATOFSIMSsurfacechemicalanalyticalstudyofrareearth
elementmineralsfrommicroflotationtestsproducts.MineralsEngineering,45,3240.
ChehrehChelgani,S.andHart,B.2014.TOFSIMSstudiesofsurfacechemistryofmineralssubjectedto
flotationAReview.MineralsEngineering,57,pp.111.
Cheng,J.,Hou,Y.,Che,L.,2007.Flotationseparationonrareearthmineralsandgangues.JournalofRare
Earth,25,6266.
Cheng,T.W.,2000.Thepointofzerochargeofmonaziteandxenotime.MineralsEngineering,13(1),105
109.
Cox, J.J., Moreton, Ch., Goode, J.R., Hains, D.H., 2010. Technical Report on the Thor Lake Project,
NorthwestTerritories,Canada.1350.
Cui, J., Hope, G. A.,Buckley, A.N., 2012. Spectroscopic investigation of the interaction of hydroxamate
withbastnaesite(cerium)andrareearthoxides.MineralsEngineering,3638,9199.
Fuerstenau D. W. and Pradip, 1984. Mineral flotation with hydroxamate collectors. In: M.J. Jones and
R.OblattEds,ReagentsintheMineralsIndustry.InstofMining&Metallurgypublication,161168.
Fuerstenau M. C., 2005. Chelating Agents as Flotation Reagents. In: Innovations in Natural Resource
Processing, Proceedings of the Jan D. Miller Symposium. Ed. By C.J. Young, J.J. Keller, M.L. Free, J.
Drelich,R.P.King,SMEPublication,LitteltonColorado,3356.
Kosmulski, M., 2009. pHdependent surface charging and points of zero charge. IV. Update and new
approach.JournalofColloidandInterfaceScience,337,439448.
Lee, K., Archibald, D., McLean, J., Reuter, M. A., 2009. Flotation of mixed copper oxide and sulphide
mineralswithxanthateandhydroxamatecollectors.MineralsEngineering,22(4),395401.
Liu, W., Wang, B., Dai, S., Ma, A., Wei, D., 2006. Current application and development prospect of
hydroximicacidinflotation.Nonferrousminingandmetallurgy,22,2527.
McNeil,M.B.,Mohr,D.W.,1993.Formationofcopperironsulfidemineralsduringcorrosionofartifacts
andpossibleimplicationsforpseudogilding.Geoarchaeology,8,2333.
Pattrick, R.A.D., Charnock, J.M., England, K.E.R. and Wright, K., 1998. Lead sorption on the surface of
ZnSwithrelevancetoflotation:Afluorescencereflexafsstudy.MineralsEngineering,11(11),10251003.
Paul,J.,Stubens,T.C.,Arseneau,G.,Maunula,T.,2009.AvalonRareMetalsInc.ThorLakeLakeZone
MineralResourceUpdate,1193.

Pavez, O., et al. 1996. Adsorption of oleate and octylhydroxamate on to rareearths minerals. Minerals
Engineering,9(3):357366.
Pavez,O.,Peres,A.E.C.,1994.Technicalnotebenchscaleflotationofabrazilianmonaziteore,Minerals
Engineering,7(12),15611564.
PradipandFuerstenauD.W.,1991.Theroleofinorganicandorganicreagentsintheflotationseparation
ofrareearthores.InternationalJournalofMineralProcessing,32(12),122.
Pradip and Fuerstenau, D. W., 2013. Design and development of novel flotation reagents for the
beneficiationofMountainPassrareearthore.Minerals&MetallurgicalProcessing,30(1),19.
PradipandFuerstenau,D.W.,1983.Theadsorptionofhydroxamatecollectorsonsemisolubleminerals,
partI:adsorptiononbarite,calciteandbastnaesite.ColloidsSurf.,8,103119.
Ren,J.,Lu,S.,Song,S.,NiuJ.,1997.Anewcollectorforrareearthmineralflotation.MineralsEngineering,
10,13951404.
Smart,R.St.C.,Gerson,A.R.,Hart,B.R.,Beattie,D.A.andYoung,C.2014.InnovationsinMeasurementof
MineralStructureandSurfaceChemistryinFlotation:Past,PresentandFuture,inInnovationsinMinerals
ProcessingandExtractiveMetallurgyEditedbyAnderson,C.,Dunne,R.,andUhrie,J.,SMEPublications,
Littleton,Colorado(USA),inpress.
Smart,R.St.C.,Skinner,W.M.,Gerson,A.R.,Mielczarski,J.,Chryssoulis,S.,Pratt,A.R.,Lastra,R.,Hope,
G.A.,Wang,X.,Fa,K.,andMiller,J.D.2007.Surfacecharacterisationandnewtoolsforresearch.InFroth
Flotation:aCenturyofInnovation.EditedbyFuerstenau,M.C.,Jameson,G.,Yoon,R.H.,SMEPublications,
Littleton,Colorado,pp.283338.
Siwek,B.,Zembala,M.,Pomianowski,A.,1981.Amethodfordeterminationoffineparticlefloatability.
InternationalJournalMineralProcessing,8,85.
Xu, J., Xu, X., Wang, J., 2002. Synthesis of 1hydroxy2naphthyl hydroximic acid and application to
collectingrareearthminerals.NonferrousMetals,54,7273.
Zhang,J.andEdwards,C.,2012.Areviewofrareearthmineralprocessingtechnology.In:44thAnnual
MeetingoftheCanadianMineralProcessors.CIM,Ottawa,79102.
Zhao C., Chen H., Yue X., 2000. Application of LF8 and LF6 Collectors in Rare Earth Beneficiation.
Chineserareearths21(3),100.