Uranium Recovery Uranium Recovery from Phosphoric Acid from Phosphoric Acid

– promising Hydro- – promising Hydro-metallurgical application of metallurgical application of

Solvent ExtractionSolvent Extraction T.K.Haldar & P.R.MohantyT.K.Haldar & P.R.Mohanty

Heavy Water BoardHeavy Water BoardDept of Atomic EnergyDept of Atomic Energy

Solvent Extraction Revisited: IIP-IIChE:NRC, New Delhi , February 2010

National PriorityNational Priority

POPULATION

1.1 Billion

GDP Growth

6.5%-7.5%

Food SecurityFood Security Projected Growth rate : 6.5% – 7%Projected Growth rate : 6.5% – 7% Rising Fertilizer ConsumptionRising Fertilizer Consumption

PP22OO55 Consumption : more than 30 lakh tpy Consumption : more than 30 lakh tpy Equivalent to 1000 MT Uranium per yearEquivalent to 1000 MT Uranium per year

1000 MT Uranium is let out to 1000 MT Uranium is let out to agricultural land every yearagricultural land every year

Accumulation is cause for ConcernAccumulation is cause for Concern Can be addressed if Uranium is removed Can be addressed if Uranium is removed

at source i.e. Phosphoric acidat source i.e. Phosphoric acid

Energy SecurityEnergy Security

Current Power demand: 250 GWeCurrent Power demand: 250 GWe Current Power generation: 200 GWeCurrent Power generation: 200 GWe

Nuclear : 4.4 GWeNuclear : 4.4 GWe

Expected demand in 2050 :1260 GWeExpected demand in 2050 :1260 GWe Projected share of Nuclear Power : 670 GWeProjected share of Nuclear Power : 670 GWe

Quantum jump in Nuclear power Quantum jump in Nuclear power generation primarily to reduce carbon generation primarily to reduce carbon emissionemission Needs Augmentation of Uranium resources Needs Augmentation of Uranium resources

besides exploiting abundant Thorium besides exploiting abundant Thorium resourcesresources

Indian Nuclear OptionIndian Nuclear Option

• Indigenous PHWR : Indigenous PHWR : • 13,000 MW by 201813,000 MW by 2018• Fuel : (Indigenous + Imported)Fuel : (Indigenous + Imported)

• Imported PWR/LWRImported PWR/LWR• 40,000 MW by 203040,000 MW by 2030• Fuel : (Imported)Fuel : (Imported)

• Indigenous FBR Indigenous FBR • 400,000 by 2050400,000 by 2050• Fuel (Indigenous U, PU & Th)Fuel (Indigenous U, PU & Th)

Why Uranium from Phosphoric Why Uranium from Phosphoric AcidAcid

Cleanup of Phosphoric Acid & lessen Cleanup of Phosphoric Acid & lessen environmental loadenvironmental load

Inadequate mineral Resource Inadequate mineral Resource QualityQuality QuantityQuantity

Considering Indian mineral sources Considering Indian mineral sources U-recovery from Phosphoric Acid U-recovery from Phosphoric Acid make economic sensemake economic sense

Indian PerspectiveIndian Perspective

POPULATIONU

in Phos.

Acid

U t

o

Nucl

ear

Fuel Cycl

e

Technology Status & Technology Status & OptionsOptions

Global scenarioGlobal scenario SX Technology deployed & provenSX Technology deployed & proven No known operating plant since 1999No known operating plant since 1999 Technology can be fine tuned for cost Technology can be fine tuned for cost

effectiveness using previous experienceeffectiveness using previous experience Indian scenarioIndian scenario

Comprehensive Technology Development, Comprehensive Technology Development, Demonstration & DeploymentDemonstration & Deployment

Credible approach towards programme Credible approach towards programme implementation for economic viabilityimplementation for economic viability

Comprehensive Comprehensive ApproachApproach

Technology development in all Technology development in all

related fields for large scale related fields for large scale

industrial deployment.industrial deployment.

Technology initiative Technology initiative

encompasses wide ranging and encompasses wide ranging and

multi-dimensional issues.multi-dimensional issues.

Research, Development, Research, Development, Demonstration & Deployment Demonstration & Deployment

(RD(RD33))

Technology for Uranium from

Phosphoric AcidSolvent

Extraction

Solvents & other inputs

Solid - liquid & Liquid-

liquid Devices

PROCESS CHEMISTR

Y

PROCESS DEVELOPME

NT

URANIUM URANIUM FROM FROM

PHOSPHORIPHOSPHORIC ACIDC ACID

ENGINEERING

CHALLENGES

ECONOMIC FEASIBILITY

PROCESS EQUIPMEN

T

SAFETY & ENVIRONMEN

T

SX Process SX Process DevelopmentDevelopment

Extraction

2(RH)2(aq)+UO2(H2PO4)2(aq) <=> (R2H)2UO2(aq) +2H3PO4 (aq)

(R2H)2UO2 (aq) <=> (R2H)2UO2 (org)

Stripping

(R2H)2UO2 (org) <=> (R2H)2UO2 (aq)

(R2H)2UO2 (aq) + 2H3PO4 (aq) <=> 2(RH)2 (aq) + UO2(H2PO4)2

SX Chemistry for U-SX Chemistry for U-recovery from Phosphoric recovery from Phosphoric

AcidAcid

CHCH22CHCH33

||

CHCH33CHCH22CHCH22CHCHCHCH22O OO O   PP  

CHCH33CHCH22CHCH22CHCHCHCH22O OHO OH | |

CHCH22CHCH33

   Structure of D2EHPAStructure of D2EHPA

  

  

RO O---H ―O RO O---H ―O OROR

P PP P

RO O― H---O OR RO O― H---O OR   

  

Hydrogen bonded dimerHydrogen bonded dimer

Metal Extractant – D2EHPAMetal Extractant – D2EHPA

P

O

O

P

O

OH2EHO

2EHO

O2EH

O2EH

D2EHPA Dimeric Anion

P

O

O-

P

O

OH

P

O-

OH

P

O

O

2EHO

2EHO

2EHO

2EHO

P

O

O-

P

O

OH2EHO

2EHO

O2EH

O2EH

O2EH

O2EH

O2EH

O2EH

-

-

P

O

O

P

O

OH2EHO

2EHO

O2EH

O2EHO

U

OP

O

O

P

O

OH2EHO

2EHO

O2EH

O2EH

O O

OO

O

O

U

U IN TETRAHEDRAL D2EHPA MATRIX

PROCESS SCHEMATICSPROCESS SCHEMATICS

SX 1ST

CYCLE

SX 2ND CYCLE

FEED PRE-TREATMENT

POST TREATMENT

RM RECOVERY

PRODUCT

WPA PRODUCER

SOLVENT REGENERATION SOLVENT REGENERATION

ACID PRE-TREATMENTACID PRE-TREATMENT

RAW WPAFLOCULATED &

FILTEREDACTIVE CARBON

TREATED

OPAQUE OD : 0.5 OD : 0.05

Process IssuesProcess Issues

Feed acid profileFeed acid profile Pre & Post treatment requirementPre & Post treatment requirement Solvent mix / selectionSolvent mix / selection

Extractant, Diluent, Synergistic Extractant, Diluent, Synergistic agent, Modifier etc agent, Modifier etc

Choice of Stripping agentChoice of Stripping agent Process control inputsProcess control inputs Waste & EffluentsWaste & Effluents

Process DevelopmentProcess Development

LAB SCALELAB SCALE MINI SCALEMINI SCALE

BENCH SCALEBENCH SCALEDEMONSTRATION SCALEDEMONSTRATION SCALE

Process Development Process Development StudiesStudies

Feed Acid grades (% PFeed Acid grades (% P22OO55)) 28%28% 42%42% 54%54%

No. of SourcesNo. of Sources 55 33 22

Qty Evaluated, MQty Evaluated, M33 500500 100100 5050

Study hours ClockedStudy hours Clocked 10001000

00

200200

00

150150

00

Solvent cycles Solvent cycles

encounteredencountered

40004000 100100

00

500500

Search For Right Search For Right Solvent(s)Solvent(s)

Promising moleculesPromising molecules Short listing (Screening & Selectivity) – in Short listing (Screening & Selectivity) – in

isolation and in synergistic combinations isolation and in synergistic combinations with other moleculeswith other molecules

Qualifying the short listed species for initial Qualifying the short listed species for initial evaluationevaluation

Selection of potential candidates for further Selection of potential candidates for further developmentdevelopment

Research, Development, Research, Development, Demonstration & Deployment (RDDemonstration & Deployment (RD33))

Technology for Uranium from

Phosphoric AcidSolvent

Extraction

Solvents & other inputs

Solid - liquid & Liquid-liquid

Devices

Identified Solvents, Quality & Identified Solvents, Quality & availability availability

Primary SolventsPrimary Solvents D2EHPA , TBP , TOPO , TAPO, DNPPAD2EHPA , TBP , TOPO , TAPO, DNPPA

Quality Quality Nuclear grade purityNuclear grade purity Impurities in ppm level detrimentalImpurities in ppm level detrimental

Secured AvailabilitySecured Availability In-house CapabilityIn-house Capability 100 MTPA D2EHPA, 190 MTPA TBP, 40 100 MTPA D2EHPA, 190 MTPA TBP, 40

MTPA TOPO / TAPO / DNPPA MTPA TOPO / TAPO / DNPPA

Development of Solvent Development of Solvent Production CapabilityProduction Capability

Process Chemistry / Synthesis routeProcess Chemistry / Synthesis route Process designProcess design Equipment Selection & detailed Equipment Selection & detailed

engineeringengineering Sound O&M PracticesSound O&M Practices Quality AssuranceQuality Assurance Emissions and EffluentsEmissions and Effluents Safety & EnvironmentSafety & Environment User Acceptability & Cost Competitiveness User Acceptability & Cost Competitiveness

Lab Scale

Pilot Scale

Industrial Scale Production Facility

The JourneyThe Journey

Bench Scale

Process Process EquipmentEquipmentSolid-liquid Solid-liquid SeparationSeparation

ClarifierBelt Filter

Research, Development, Research, Development, Demonstration & Deployment (RDDemonstration & Deployment (RD33))

Technology for Uranium from

Phosphoric AcidSolvent

Extraction

Solvents & other inputs

Solid - liquid & Liquid-liquid

Devices

Process EquipmentProcess EquipmentLiquid-liquid ContactorsLiquid-liquid Contactors

Mixer-

Settler

Centrifugal

ExtractorRotating

disc Column

Engineering ChallengesEngineering Challenges

Materials of constructionMaterials of construction Plant lay outPlant lay out Regulatory compliancesRegulatory compliances Seamless integration with Seamless integration with

conventional Fertiliser Industryconventional Fertiliser Industry EconomicsEconomics

Environmental IssuesEnvironmental Issues

Effluent ManagementEffluent Management

Local Statutory requirement Local Statutory requirement

Radiological Monitoring and Radiological Monitoring and

ProtectionProtection

Taking a Call by Indian Nuclear Taking a Call by Indian Nuclear CommunityCommunity

Concern for environment Concern for environment

voluntary, not regulatoryvoluntary, not regulatory Potential Energy Resource Potential Energy Resource

Exploitation Vs. WastageExploitation Vs. Wastage Investment Decision Investment Decision

Economic & StrategicEconomic & Strategic Challenge for Nuclear CommunityChallenge for Nuclear Community

Growth of SX - ProcessGrowth of SX - Process