Enrichment of 48 Ca ~liquid-liquid extraction by “micro-reactor” ~ R. Hazama, Y. Sakuma, Y. Ogata, R. Miyake, M. Tokeshi, M. Akita 岩沼 Dec18, 2010 Separation with a crown ether

OH H3CH3C CH 3 o o o o o o OH H3CH3C CH 3 o o o o o o HO Microchip Resin Benzo or Di-benzo or Di-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 (Ca 2+ )  How well the cation fits into the crown ring  Liquid(aq-salt)-liquid(org-crown)/solid(resin) extraction in isotopic equilibrium O OO O OO CC C C C C CC Dicyclohexano 18- crown-6 Ca LiquidSoild Ca

A-typeFH-type Solid./Liq. Increase Ca content   doesn’t change Liq./Liq.  (α )= ？？？ 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) Eichrom or IBC Resin = SuperLig 樹脂 40 Ca 2+ (aq)+ 48 CaL 2+ (org) 48 Ca 2+ (aq)+ 40 CaL 2+ (org) Crown-chloroform organic CaCl 2 aqueous phase 40 Ca 48 Ca

Conventional Chemical Process Microchemical Process extraction separation enrichment mixing reaction heating  TAS (Micro Total Analysis System) & Synthetic chemistry Lab-on-a-chip Chemistry

Advantages （１） multi-phase flow  ideal reaction/extraction field （２） Large interfacial area  >10 2 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-up Disadvantage  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/ year price control over temp./reaction time, it can achieve high 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 m 2 /s typical # for molecular in water) W=100  m  S/V=200 ! W=100  m  T=10s ! (10μm  T=0.1s!) W W2W2

100  m wide,40  m deep, and 40cm length A~200/cm -1 T~10s

Organic phases were devided into small droplets and 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~10 4 /cm -1 T~4ms w=2~3μm? mixing zone (2  15 microchannels: 60  m width, 150  m depth, separated by 50  m walls,  =3250  m  150  m length 25mm)

LLE iteration Concentration of Ca ion Batch Micro-reactor ± ± ± ± ± ± (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 48 Ca/ 40 Ca = 2  44 Ca/ 40 Ca STD Open: 2 ℃ Filled: 20 ℃ α ＝１．００７ ± ０．００２ Ratio= ０．０２１５４ ± ０．０００１１ DC18C8 Room temp. 20 ℃ DC18C8 Low temp. 2 ℃ α ＝１．００６ ± ０．００２ Ratio= ０．０２１５０ ± ０．０００１１ R 0 = 44 Ca/ 40 Ca = ０．０２１５７ α ～１．０１２ ～１．０１４

  (α )=1.003  200m & 10 days  48 Ca×1.34  Absorption of Ca depends on concentration of hydrochloric acid(9M HCl)   (α )=1.014 ×2 (1.008 by Jepson)   ×1.34 requires ~20 LLE (~2days)  wide variety/option  Ca concentration one order improve! with ~1/6 time:13min by microreactor Liq./Liq. Solid./Liq. J. Inorg.nucl.Chem38(1976)1175