Thermal Cycling Absorption Process Overview

Xin Xiao, Benton Randall, Henry T. Sessions, Robert Allgood, Dave BabineauSavannah River National Laboratory

Overview

• How does TCAP Work?

• TCAP History

• State of the Art Technology

• Typical Performance

• In House Expertise and Capability

• TCAP Feature Summary

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Tritium Processing at SRS - The Largest Metal Hydride Based Tritium Facility in the World

MH=Metal Hydrides: Pd, Pd/k, LaN5-xAlx, Ca1-yMmyNi5, Ti, U

Reservoirs Unloading

MH Primary Separator

Diffusers

Mix Tanks

Reservoirs Loading &

Sealing

PumpsMH T2 & D2

Storage

Vacuum Pumps

MH Feed Bed

MH T2

Storage

MH D2

Storage

MH TCAPIsotope

Separation

MechanicalCompressors

MH Compressors

He-3

Newly Loaded

ReservoirsMHLong-TermT2 Storage

MH Transport Vessels

Glovebox T2

Stripping System

Gloveboxes

Catalyst Bed Zeolite Bed Mg BedGloveboxesTo Isotope Separation

Compressor

Cryosorption

Gas Cylinder

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TCAP with passive-PFR

TCAP with active-’PFR’

Feed

Product

Feed

Product

Raffinate

Raffinate

Pd/k

Pd/k

Act

ive

PFR

Pass

ive

PFR

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Isotopic Effect Based on Material Property

Palladium favors lighter hydrogen isotope Molecular Sieve favors heavier hydrogen isotope

5

TgasDgas

TsolidDsolid

1

Pd

Other Hydrides

Colder

0

20

40

60

80

100

120

140

160

0 200 400 600 800Absolute Pressure, mmHg

Ads

orbe

d Q

uant

ity, S

TP c

c/g

UOP 13X, D2UOP 13X, D2UOP 13X, H2UOP 13X, H2

TCAP Development History• TCAP concept invented at SRL 1980• Experimental TCAP achieved 97% purity (D2, H2 ) 1983• Prototype TCAP achieved 99% purity (D2, H2) 1989• Pilot TCAP demonstrated (production-configured) 1993• Production TCAP achieved target T2/D2 separation 1994• Compact TnT design tested at LANL 2001• Batch Cryogenic distillation column replaced by TCAP 2004• Comp.-free CTC concept developed, 1/10th footprint 2006• Comp.-free CTC experiment reached 4,000 cycles 2009• Inverse Column achieved 2X+ capacity & higher purity 2009• Mini-TCAP for Shine Medical Technologies 2013• Micro-TCAP (batch) for LLE (U. Rochester) 2013• Plant-Configured mini-TCAP reached 8,000 cycles 2018

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Representation of TCAP Footprint Reduction

CTC-TCAP (1/10th current footprint) Mini-TCAP Micro-TCAPNew TCAP technology continues to evolve in miniature designs for diversified applications

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TCAP for SHINE Medical Technologies

Mini-TCAP constructed by SRNL

Linear Accelerator in SHINE for medical isotope production

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TCAP for LLE, University of Rochester

Micro-TCAP constructed by SRNL

Laser Target Shot in Laboratory for Laser Energetics for Fusion Study

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Micro-TCAP Configuration

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TCAP Typical T and P Cycles

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TCAP Concentration Profile

Micro-TCAP Concentration Profile (Feed V16)

0

20

40

60

80

100

0 1000 2000 3000 4000 5000Column Gas Quantity, std cc

Con

cent

ratio

n, %

D%H%

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Extensive Evaluation for Component Selection

– LN2 control valves– Process valves:

• Tritium compatibility• Pressure rating• Performance• Durability

– Pressure transducers– Thermocouples– Insulation

Components meet ASME B31.3 and are tritium compatible

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MS Column Cooling

-200

-180

-160

-140

-120

-100

-80

-60

916 921 926 931 936 941 946 951 956Time, min

Tem

pera

ture

, °C

Ave MS Temp - PID controlValve response - PID controlAve MS Temp - LN2 exhaust controlValve response - LN2 exhaust control

LN2 Control Algorithm

MS column

Coolant LN2

Coolingcoil

Coolant N2 gas

Heater

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Separation Enhanced by Reactive Equilibrium

15

o-H2

p-H2

HDequilibrated

Why Us? - Team with Track of Records and Expertise• Discovery of deuterium 1931

• Discovery of tritium 1934

• TCAP concept invented at SRL 1980

• SRS Isotope Separation

⁻ Thermal diffusion 1957-1986

⁻ Fractional absorption1964-1968

⁻ Cryogenic distillation 1967-2004

⁻ TCAP 1994- present

TCAP Team 2017

TCAP (Thermal Cycling Absorption Process) for hydrogen isotope separation

TCAP Team 1985

TCAP 2012

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Water Isotope Separation Under Development

GO

MFC

Water feed

BPR

V-3

V-1

sample1(feed water)

18' Column

Liquid pump

H2

sample2(effluent water)

PSV1

V-2Cold trap

sample3(recycle back

to feed)3A d

ryer

vent

TCAP(optional)

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Energy Secretary Ernest Moniz in the TCAP Lab

SRNL’s Steve Xiao (from left), Sharon Redd and Tommy Sessions explain the research and development process behind SRNL’s Thermal Cycling Absorption Process (TCAP) for Secretary Moniz in July 2014. SRNL has continually improved TCAP’s ability to enrich tritium gas in a smaller space, and in a more cost-effective process.

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Energy Secretary Rick Perry in the TCAP Lab

Savannah River National Laboratory (SRNL) Director of Defense Programs Science and Technology David Babineau explains the Thermal Cycling Absorption Process (TCAP) to Energy Secretary Rick Perry in February 2018. TCAP has reduced the footprint needed to separate hydrogen isotopes by up to 10 times while saving operational costs and improving performance.

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TCAP Technology Licensed to Greenway Energy

Savannah River National Laboratory (SRNL) Director Vahid Majidi and President of Greenway Energy Scott Greenway signed TCAP license agreement. Standing in the Backrow are Director of Defense Programs David Babineau, inventors Henry T. Sessions and Steve Xiao.

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Isotope Separation for Tritium: Past, Present and Future

Past: 23 ft. Cryogenic Distillation Column

Cryogenic Distillation • 23 Feet Tall• Significant Supporting Infrastructure

• Helium refrigeration• Liquid nitrogen cooling jacket

• Large inventory of tritium• Batch mode operation• Difficult to control

Present: Thermal Cycling Absorption Process

Thermal Cycling Absorption Process • About three feet in length and diameter• Small enough to be placed in glovebox• Reduced material-at-risk by 27X• Reduced tritium environmental emissions by 1000X• Continuous mode operation• Reduction in supporting infrastructure• Hot and cold nitrogen refrigeration system

Mini-TCAP• < 1/10th footprint of present TCAP• ¼ heat load• Further reduces tritium at risk by 2/3• Once through liquid nitrogen cooling• Electric heating

Past

Present

Future

Future: Mini-TCAP

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Summary: TCAP Features

Separation by chromatographyHydrogen itself as carrier gasExcellent radioactive confinementReprocess gas in column repeatedlyHD re-equilibrium / separation

VersatilityScale by throughputImpurity rejectionEnergy efficient

Simple design & advanced control logicNo mechanical moving parts besides valvesInherently safe / extra long lifeRobust and fault proof

Easily beat deuterium natural abundance (~ 150 ppm)

Pressure swingTemperature SwingHydride vacuum pumpHydride pressure pumpHydride interim storage

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