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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