Enrichment of Enrichment of 4848CaCa~liquid-liquid extraction ~liquid-liquid extraction

by “micro-reactor” ~by “micro-reactor” ~

R. Hazama, Y. Sakuma, Y. Ogata,R. Miyake, M. Tokeshi, M. Akita

二重ベータ崩壊研究懇談会 @ 岩沼 Dec18, 2010

Separation with a crown ether

OH

H3C CH3o

oo

oo

o

OH

H3C CH3o

oo

oo

o

HO

HO

MicrochipResin

Benzo or Di-benzo orDi-cyclo or bare-18C6

Total # of atoms in the ring # of oxygen atoms in the ring

DC18C6

Held by electrostatic attraction between

negatively charged O- of the C-O dipoles & cation

(Ca2+)

How well the cation fits into the crown ring

Liquid(aq-salt)-liquid(org-crown)/solid(resin)

extraction in isotopic equilibrium

O

O O

O

OO

C C

C

C

C

C

C CDicyclohexano 18-

crown-6

Ca2+

- -

- -

- -

Liquid Soild

Ca2+

- -

- -- -

A-type FH-type

0.088

0.0034

0.000425

-3.3716

Solid./Liq. Increase Ca content doesn’t change

Liq./Liq.(α40

48)= ？？？ by pure organic solvent =1.008 by water-alchohol mixture

HCl aqueous solution: ε~1.003

Jepson & DeWitt, J. Inorg.nucl.Chem38(1976)1175 (chloroform-methanol)

LLE by Microchannel/reactor Fast & Highest

conversion synthesis Aqueous-organic multi-

phase flow & process amount

Column chromatography using crown ether resins

Multi-stage process Slow & low conversion

Packed column(stationary phase)

Ca solution: Analyte(mobile phase)

Eichromor IBC Resin

=SuperLig 樹脂

40Ca2+(aq)+48CaL2+(org)

48Ca2+(aq)+40CaL2+(org)

Crown-chloroform organic

CaCl2 aqueous phase

40Ca

48Ca

Conventional Chemical

Process

MicrochemicalProcess

extraction

separation enrichment

mixingreaction

heating

TAS(Micro TotalAnalysis System) &Synthetic chemistry

Lab-on-a-chipChemistry

Advantages（１） multi-phase flow ideal reaction/extraction field（２） Large interfacial area >102 x stirring high conv.（３） short diffusion distance fast reaction speed（４） small heat capacity uniform/fast temp.control（５） small flow output toxic manage ・ fast heating（６） piling/numbering-up technology easy to scale-

upDisadvantage small output/1 chip piling-up（１） cheap microreactor plastic vs. glass（２） piling-up technology & stable flow technology

Medical supplies/medicine(painkiller:aspirin) ~ 72 ton/ yearprice control over temp./reaction time, it can achievehigh reaction yield rates that were not possible with the conventional type

Specific interfacial area（ surface to volume ratio:S/V ）

S/V = dL/(wdL/2)= 2/

Diffusion time

T= /D (D=10-9 m2/s typical # for molecular in water)

W=100m S/V=200 !

W=100m T=10s ! (10μm T=0.1s!)

W

W2

100m wide,40m deep,and 40cm length

A~200/cm-1

T~10s

Organic phases were devided into small dropletsand flowed inside the aqueous tube

A larger interfacial area was formed not only in both ends of the segments, but also around the organic droplets.

A~104/cm-1

T~4ms

w=2~3μm?

mixing zone(2 15 microchannels:

60m width, 150m depth,separated by 50m walls, =3250m 150m length 25mm)

LLE iteration

Concentration of Ca ion

Batch Micro-reactor

3 0.5636±0.0078 1.7165±0.1028

4 0.0168±0.0034 0.2882±0.0254

5 0.0255±0.0044 0.2571±0.0182

(ppm)

Thermo Scientific iCAP6500 (ICP-OES(AES))

400mL by 30ml/min for org. ~13min(40mL by 3ml/min for aq. ) ~1/6 ×batch

ＤＢ１８Ｃ６

ＤＣ１８Ｃ６

１８Ｃ６

crown-ether organic solvent

chloroform

Dichloromethane

temperature

Room temp.（２０℃）

Low temp.（２℃）

Nitrobenzene ７℃

Isotopic Analysis by Reaction-cell ICP@JAMSTEC

48Ca/40Ca= 2 44Ca/40Ca

STD

Open: 2 ℃Filled: 20 ℃

α ＝１．００７ ± ０．００２Ratio= ０．０２１５４ ± ０．０００１１

DC18C8Room temp. 20 ℃

DC18C8Low temp. 2 ℃

α ＝１．００６ ± ０．００２Ratio= ０．０２１５０ ± ０．０００１１

R0=44Ca/40Ca

= ０．０２１５７

α ～１．０１２ ～１．０１４

(α4048)=1.003

200m & 10 days 48Ca×1.34

Absorption of Ca depends on concentration of hydrochloric acid(9M HCl)

(α4048)=1.014

×2 (1.008 by Jepson)×1.34 requires ~20 LLE

(~2days)wide variety/optionCa concentration one order improve! with

~1/6 time:13min by microreactor

Liq./Liq.Solid./Liq.

J. Inorg.nucl.Chem38(1976)1175