稀土元素-从煤基材料中回收 RARE EARTH ELEMENTS – RECOVERY FROM COAL-BASED MATERIALS

ICSC/334NOVEMBER2024

RAREEARTHELEMENTS

-RECOVERYFROM

COAL-BASEDMATERIALS

DRSTEPHENMILLS

RAREEARTHELEMENTS–

RECOVERYFROM

COAL-BASEDMATERIALS

INTERNATIONALCENTREFORSUSTAINABLECARBON

EPSILONHOUSE

THESQUARE

GLOUCESTERBUSINESSPARK

GLOUCESTERGL34AD

UNITEDKINGDOM

+44[0]2039053870

WWW.SUSTAINABLE-CARBON.ORG

INTERNATIONALCENTREFORSUSTAINABLECARBON

RAREEARTHELEMENTS-RECOVERYFROMCOAL-BASEDMATERIALS

3

AUTHORDRSTEPHENMILLS

ICSCREPORTNUMBERICSC/334

ISBN978-92-9029-657-7

©INTERNATIONALCENTREFOR

SUSTAINABLECARBON

PUBLICATIONDATENOVEMBER2024

INTERNATIONALCENTREFORSUSTAINABLECARBON

RAREEARTHELEMENTS-RECOVERYFROMCOAL-BASEDMATERIALS

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PREFACE

ThisreporthasbeenproducedbytheInternationalCentreforSustainableCarbon(ICSC)andisbasedonasurveyandanalysisofpublishedliteratureandoninformationgatheredindiscussionswithinterestedorganisationsandindividuals.Theirassistanceisgratefullyacknowledged.Itshouldbeunderstoodthattheviewsexpressedinthisreportareourownandarenotnecessarilysharedbythosewhosuppliedtheinformation,norbyourmemberorganisations.

TheInternationalCentreforSustainableCarbonwasestablishedin1975andhascontractingpartiesandsponsorsfromAustralia,China,Italy,Japan,andSouthAfrica.

TheoverallobjectiveoftheInternationalCentreforSustainableCarbonistocontinuetoprovideourmembers,theInternationalEnergyAgency(IEA)WorkingPartyonFossilEnergyandotherinterestedpartieswithdefinitiveandpolicy-relevantindependentinformationonhowvariouscarbon-basedenergysourcescancontinuetobepartofasustainableenergymixworldwide.Theenergysourcesinclude,butarenotlimitedtocoal,biomassandorganicwastematerials.OurworkisalignedwiththeUNSustainableDevelopmentGoals(SDGs),whichincludetheneedtoaddresstheclimatetargetsassetoutbytheUnitedNationsFrameworkConventiononClimateChange(UNFCCC).Weconsiderallaspectsofsolidcarbonproduction,transport,processingandutilisation,withintherationaleforbalancingsecurityofsupply,affordabilityandenvironmentalissues.Theseincludeefficiencyimprovements,loweringgreenhouseandnon-greenhousegasemissions,reducingwaterstress,financialresourcing,marketissues,technologydevelopmentanddeployment,ensuringpovertyalleviationthroughuniversalaccesstoelectricity,sustainability,andsociallicencetooperate.Ouroperatingframeworkisdesignedtoidentifyandpublicisethebestpracticeineveryaspectofthecarbonproductionandutilisationchain,sohelpingtosignificantlyreduceanyunwantedimpactsonhealth,theenvironmentandclimate,toensurethewell-beingofsocietiesworldwide.

TheInternationalCentreforSustainableCarbonisaTechnologyCollaborationProgrammeorganisedundertheauspicesoftheInternationalEnergyAgency(IEA)butisfunctionallyandlegallyautonomous.Views,findingsandpublicationsoftheInternationalCentreforSustainableCarbondonotnecessarilyrepresenttheviewsorpoliciesoftheIEASecretariatoritsindividualmembercountries.

NeithertheInternationalCentreforSustainableCarbonnoranyofitsemployeesnoranysupportingcountryororganisation,noranyemployeeorcontractoroftheInternationalCentreforSustainableCarbon,makesanywarranty,expressedorimplied,orassumesanylegalliabilityorresponsibilityfortheaccuracy,completenessorusefulnessofanyinformation,apparatus,productorprocessdisclosed,orrepresentsthatitsusewouldnotinfringeprivatelyownedrights.

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ABSTRACT

Thisreportconsidersthestrategicimportanceandgrowingglobaldemandforrareearthelements(REEs),vitalcomponentsformanyhigh-techconsumerdevicesanddefenceapplications.Theyarealsoacrucialcomponentoftheenergytransitionandareusedinrenewableenergytechnologiessuchassolarpanels,windturbines,electrolysers,andelectricvehicles.

ManystudieshavefocusedontherecoveryREEsfromdifferentcoal-relatedmaterialsincludinghardcoalandlignite,coalrefuse,minedrainage,andcoalcombustionby-productssuchasflyash.AwiderangeoftechniquesforextractingREEshavebeenproposedortrialled,suchasphysicalbeneficiation,acidleaching,ion-exchangeleaching,bioleaching,thermaltreatment,alkalitreatment,solventextraction,andmorenovelconcepts.

Coalgeologyandchemistry,chemicalengineering,processdevelopment,andextractivemetallurgysupportthedevelopmentofpossibleextractionprocesses.DatageneratedbythesecombinedeffortsareallowingvariousREErecoveryconceptstoprogressfromfeasibilitystudiestolaboratory-andpilot-scaleinvestigations.Severalprocessesaremovingtowardsinitialcommercialproduction.However,manyprocesseshaveonlybeenevaluatedatlimitedscaleandlackharddataontheireconomicviabilityandpossibleenvironmentalimpact.Somerequirefurthertechnicaldevelopmentandoptimisation.Morefundamentalresearchcontinuesintorecoveryprocesseslessreliantontheuseofaggressiveconditionsthatoftenincludetheuseofstrongacids,alkalis,andorganicsolvents.

REErecoveryfromcoal-basedmaterialsisanevolvingfield.Significantachievementshavebeenmadeduringthepastdecade,buttheirextractionremainschallenging.Foranyrecoveryschemetobeconsideredviable,itwillneedtostriketherightbalancebetweenefficiency,cost,andenvironmentalimpact.ThisreportexaminesthemoreestablishedmethodsforextractingREEsfromcoal-basedmaterials,reviewssomeofthemorepromisingnoveltechniquesbeingdeveloped,andconsidersprogressbeingmadetowardsthepossibilityofthembecomingfeasiblealternativestoconventionalmineralores.

ThereisabigincentivetoachieveviableREErecoveryfromcoal-basedmaterials–successfuldevelopmentwouldhelpdiversifysources,easeconcernsovercurrentandfuturemarketdomination,andhelpprogresstowardstechnologieseffectiveinmitigatingclimatechange.

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RAREEARTHELEMENTS-RECOVERYFROMCOAL-BASEDMATERIALS

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ACRONYMSANDABBREVIATIONS

AMD

acidminedrainage

CEM

cationexchangemembrane

CIL

CoalIndiaLtd

CORE-CM

Carbonore,rareearth,andcriticalmaterials

CRM

criticalrawmaterial

DOD

DepartmentofDefense,USA

DOE

DepartmentofEnergy,USA

DRWP

drinkingwatertreatmentplant

EC

EuropeanCommission

EDR

electrodialyticrecovery

ERMA

EuropeanMaterialsAlliance

EU

EuropeanUnion

EV

electricvehicle

FEED

frontendengineeringdesign

FGD

fluegasdesulphurisation

FJH

flashJouleheating

FTIR

FourierTransformedInfraredSpectroscopy

HREE

heavyrareearthelements

JOGMEC

JapanOrganizationforMetalsandEnergySecurity

LEM

liquidemulsionmembrane

LM

liquidmembrane

LREE

lightrareearthelements

LTP

lowtemperatureplasma

MREE

mediumrareearthelements

MRT

molecularrecognitiontechnology

NETL

NationalEnergyTechnologyLaboratory,USA

ppm

partspermillion

RD&D

research,developmentanddemonstration

RE

rareearth

REE

rareearthelement

REM

rareearthmetals

REO

rareearthoxides

ROM

run-of-mine

SCF

supercriticalfluid

SLM

supportedliquidmembrane

UND

UniversityofNorthDakota,USA

Note:allmonetaryvaluesareinUnitedStatesdollars($)unlessotherwisestated.

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UNITS

°C

degreesCelsius

g

grammes

Gt

gigatonnes

kg

kilogrammes

kg/h

kilogrammesperhour

kt

kilotonnes

kt/y

kilotonnesperyear

kW

kilowatt

kWh

kilowatt-hour

m3

cubicmetre

m

metres

mg/kg

milligrammeperkilogramme

Mt/y

milliontonnesperyear

MW

megawatt

ppm

partspermillion

t

tonne

t/d

tonnesperday

t/h

tonnesperhour

t/w

tonnesperweek

t/y

tonnesperyear

wt%

weightpercent

CHEMICALS

CaO

calciumoxide

CaSO4

calciumsulphate

HCl

hydrogenchloride

HNO3

nitricacid

H2SO4

sulphuricacid

NaOH

sodiumhydroxide

Na2CO3

sodiumcarbonate

Na2O2

sodiumperoxide

sCO2

supercriticalcarbondioxide

TBP

tributylphosphate,C12H27O4P

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CONTENTS

PREFACE4

ABSTRACT5

ACRONYMSANDABBREVIATIONS6

CONTENTS8

LISTOFFIGURES10

LISTOFTABLES11

EXECUTIVESUMMARY12

1INTRODUCTION15

1.1WhatareREEs?15

1.2WhereareREEsfound?17

2THESTRATEGICIMPORTANCEOFREES19

2.1China19

2.2EU21

2.3Australia23

2.4Japan23

2.5USA23

2.6Summary26

3CONVENTIONALREEMINING27

3.1EnvironmentalimpactsofREEminingandproduction29

3.2Summary32

4THEPRESENCEOFREESINCOAL33

5RECOVERINGREESFROMCOAL36

6REESINCOALWASTESANDBY-PRODUCTS38

6.1Potentialadvantagesofusingcoalwastesandby-products38

6.2Flyash39

6.3TreatmentforrecoveryofREEs41

6.4USA44

6.4.1UniversityofNorthDakota46

6.4.2UniversityofKentucky48

6.4.3RamacoResourcesInc49

6.4.4OtherUSprojects49

6.5EU50

6.5.1Germany50

6.5.2Poland50

6.5.3Serbia50

6.5.4Greece50

6.6SouthKoreaandVietnam51

6.7SouthAfrica51

6.8Australia52

6.9India52

6.10Summary52

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7TECHNIQUESFORREERECOVERYFROMCOALWASTES53

7.1Physicalseparationmethods53

7.2Pretreatmenttechniques54

7.2.1Alkaliandthermalpretreatment54

7.2.2Roasting(thermalactivation)55

7.2.3Chemical/thermalpretreatment55

7.2.4Microwavetreatment55

7.2.5Plasmaassisttechnology56

7.3Promisingnoveltechniquesproposedorindevelopment57

7.3.1FlashJouleHeating(FJH)58

7.3.2Ultrasound-assistedalkali-acidleaching58

7.3.3Magneticseparationandzeolitisation58

7.3.4Ionchromatography59

7.3.5Selectivehalogenationandreductionusingmixedhalidesalts60

7.3.6Ionicliquidextraction61

7.4Supercriticalextractiontechniques62

7.5Liquidmembraneseparation64

7.6Molecularrecognitiontechnology65

7.7ElectrodialyticrecoveryofREEsfromcoalash66

7.8Electrochemicalextraction67

7.9Aciddigestionandelectrowinning68

7.10Biological-basedtechniques69

7.10.1Biomining69

7.10.2Bioleaching69

7.10.3Biosorption71

7.11Summary72

8RECOVERYOFREESFROMACIDMINEDRAINAGE74

8.1USA75

8.1.1WestVirginiaUniversity75

8.1.2PennStateUniversity76

8.1.3OhioStateUniversity77

8.1.4RTIInternational,Cerahelix,andVeoliaWater/Montrose77

8.2AMDresearchinothercountries78

8.3Summary79

9CONCLUSIONS80

10REFERENCES84

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LISTOFFIGURES

Figure1Rareearthelements16

Figure2Rareearthprices2021-24(basedonPr-Ndoxide)18

Figure3China’sdominanceofglobalREEmarkets20

Figure4BreakdownofChina’sREEprocessingandpermanentmagnetproductiondominance21

Figure5TheMountainPassfacilityinCalifornia25

Figure6ProductionstagesforconventionalREErecovery29

Figure7REEproductioninChina31

Figure8OutflowfromrareearthsmeltingplantnearBaotou,China31

Figure9TheNETLREEprogramme45

Figure10OverviewofNETLREEprogramme46

Figure11UniversityofNorthDakotaREErecoverypilotfacility47

Figure12UniversityofNorthDakota’sproposedflowsheetforREEextractionfromlignite47

Figure13Plasmaassisttechnology57

Figure14Magneticseparationandzeolitisationflowsheet59

Figure15PhoenixTailingsselectivehalogenationandmixedhalidesaltsprocess60

Figure16REErecoveryfromflyashusingsupercriticalfluids62

Figure17REErecoveryusingsupercriticalfluidswithtributylphosphate(TBP)63

Figure18ElectrodialyticrecoveryofREEsfromcoalash67

Figure19LLNLbiosorptionsystem72

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LISTOFTABLES

Table1TopREEproducingcountries,202317

Table2REErecoverymethodsfromprimarysources28

Table3REErecoverymethodsfromcoal-basedmaterials28

Table4REEdataofcoalashfrommajorglobalcoal-consumingcountries40

Table5AdvantagesanddisadvantagesofmethodsusedforREErecoveryfromcoal-related

materials43

Table6ExamplesofAMDresearch79

EXECUTIVESUMMARY

INTERNATIONALCENTREFORSUSTAINABLECARBON

RAREEARTHELEMENTS-RECOVERYFROMCOAL-BASEDMATERIALS

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EXECUTIVESUMMARY

Thereportconsidersthestrategicimportanceandgrowingglobaldemandforrareearthelements(REEs),vitalcomponentsformanyhigh-techconsumerdevicesanddefenceapplications.Theyarealsoacrucialelementoftheenergytransitionandareusedinrenewableenergytechnologiessuchassolarpanels,windturbines,electrolysers,andelectricvehicles.

GlobalreservesofREEsarecurrentlyestimatedataround130Mt.Productionhasincreasedsignificantlyduringthepastdecadefromjustabove100ktin2013,to350ktin2023,anupwardtrendthatisexpectedtocontinue.REEsareminedpredominantlyinChina,Vietnam,Brazil,Russia,India,Australia,andtheUSA,althoughseveralothercountrieshavealsoidentifiedreservesbutarenotyetinproduction.TheglobalmarketforREEswasUS$5.3billionin2021andisprojectedtoincreasetoUS$9.6billionby2026.Thewindturbinemarketisexpectedtoaccountforaround30%oftheglobalgrowthintheuseofrareearth(RE)magnetsinthecomingyears.

ChinadominatesglobalproductionandsupplyofREEs,whichcausesconcernsovercostandsecurityofsupply,especiallyinwesternnations.China’spositionhasallowedittoperiodicallyfloodorotherwisecontrolglobalREEmarketssincethe1980s;REEs’supplyandpriceshavebeeninfluencedbydomestictaxpolicies,quotasystems,andexportrestrictions.Thecountryhasalsostockpiledcriticalmaterialsduringmarketgluts.ChinacontinuestotightenitsgripontheminingandrefiningofREEsandinternationalmarketsviatheintroductionofmeasuresincludingfurtherexportrestrictionsandtightercontroloverstate-ownedcompanies.Againstthisbackground,manycountriesareattemptingtodeveloptheirownsourcesandestablishalternativesupplychainsasamatterofnationalsecurity.

Alongsideproductionfromnaturalmineralsources,focushasincreasedonre