purification of n2 and ar · 2005. 9. 1. · zpurification of n 2 from kr by adsorption is possible...
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1
Purification of N2 and Ar
Hardy Simgen, MPIK Heidelberg
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Hardy Simgen, ββ-meeting, 26. + 27.1.04 Page 2
Outline
RequirementsGas purification by adsorptionN2 purificationAr purificationTechniques for analysisSummary
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Production
N2, Ar are produced fromair by rectification
Traces of atmosphericnoble gases remain in final product
Final purity depends on individual plant
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Radioactive noble gas nuclides in the air
0.5 µBq/m3 air50 µBq/m3 Ar
cosmogenic42Ar
10 to >100 Bq/m3 airPrimordial 238U222Rn
1.4 Bq/m3 air1.2 MBq/m3 Kr
235U fission (nuclear fuelreprocessing plants)
85Kr
17 mBq/m3 air1.8 Bq/m3 Arcosmogenic39Ar
Activity concentration (STP)Sources
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Requirements222Rn:
MC simulations [Baudis 2002]:0.5 µBq/m3 N2 (STP) = 6⋅10-5 events/(kg⋅y⋅keV)
BOREXINO has achieved this goal
42Ar:MC simulations [Schönert]:50 µBq/m3 N2 (STP) = 4⋅10-5 events/(kg⋅y⋅keV)
42Ar naturally low enough
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Requirements
Q-value of 39Ar and 85Kr below 700 keV:
But dead-time problem when Ar scintillation isused (slow decay time: 1 µs)
Assume 30 m3 active volume39Ar rate: 50 kHz OK!85Kr rate not higher ⇒ ≤1 ppm krypton required
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Gas purification byadsorption
Applied when highest purities are required
Based on different binding energies
Pore size distribution is crucial
Activated carbon suited for most applications
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Henrys Law
n = H · p
n = number of moles adsorbed [mol/kg]p = partial pressure of Kr [Pa]H = Henry coefficient [mol/(kg·Pa)]
valid for low partial pressures
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Single componentadsorption model for H
S. Maurer, Ph.D. thesis, TU München (2000)Adsorption on activated carbonbased on van-der-Waals equation
simple empirical formula derived:
[ ][ ][ ]
−⋅
+−=
⋅
5.17barK
K8105.0exp
Pakgmol
C
C
PT
TH
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Single componentadsorption model for H
1E+1447.663377Rn
2E+528.255209Kr
2E+221.634126N2
2E+221.649151Ar
H [mol/(kg·Pa)]@ 77 Kelvin
TC·PC-0.5
[K·bar-0.5]PC
[bar]TC
[K]Gas
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N2 purification
Lots of know-how at MPI-K (BOREXINO)
Removal of Ar not possible by adsorption
Rn purification possible but problem with222Rn emanation
Highly pure synthetic carbon „Carbo Act“222Rn emanation <0.3 mBq/kg
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N2 purification
222Rn <0.3 µBq/m3 N2
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Purification of N2 from Kr
Single component adsorption model fails forbinary system N2/Kr
„Competition“ between N2 and Kr foravailable adsorption sites
Henry coefficient for Kr adsorption drops from~102 to ~10-4 when N2 is present
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H and pore sizes
0.01
0.1
1
10
100
1000
10000
100000
1e+06
1e+07
1e+08
1e+09
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
Hen
ry c
oeffi
zien
t H [
mol
/(kg*
Pa) ]
Pore size b [ Angstroem ]
Nitrogen
Krypton
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Pore size distributions
Activated CarbonSkeleton
pore size [Å]
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Purification of N2 from Kr
Further improvment by gas phase adsorption at low temperatures
Pores and gas phase lead to H ~1 mol/kg/Pa
More than 500 m3 of N2 (STP) can be purifiedwith ~1 kg of adsorber (V=H⋅R⋅T⋅m)
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Purification of N2- Summary -
Rn removal no problem
Ar removal impossible
Kr removal technically feasible but requireslow temperature gas phase adsorptionPore size-tuned carbon adsorbers
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Single componentadsorption model for H
1E+1447.663377Rn
2E+528.255209Kr
2E+221.634126N2
2E+221.649151Ar
H [mol/(kg·Pa)]@ 77 Kelvin
TC·PC-0.5
[K·bar-0.5]PC
[bar]TC
[K]Gas
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Purification of Ar
(Almost) no difference between Ar and N2for adsorption on activated carbon
However T(LAr) = T(LN2) + 10K
Rn removal no problem
Kr removal for Ar even more challengingthan for N2 (especially for large amounts)
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Techniques for analysis- Nitrogen -
Rn, Ar, Kr analysis in N2 performed at MPI-K within BOREXINO
Rn ↔ low background proportional countersDetection limit: 30 µBq
Ar, Kr ↔ noble gas mass spectrometerDetection limits: 1 ppb for Ar
0.1 ppt for Kr
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Noble gas purification line
getter-pump
connections for differentgases (Kr, Ar, Xe, N , CH , ...)2 4
main line
highly pureold xenon
Toepler pump mercurymanometerto main pump
flow meter
carbon trap forhelium-purification
sample container(dismountable)
NaOH-trapagainst CO2
silicageltrap
smallcarbon
trapbig
carbontrap
chromosorbtrap
gasexit
exchangeablechromatography column
helium
port forproportionalcounter
topump
gasexit
thermistor
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Noble gas purification
line
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Mobile RadonExtraction
Unit (MoREx)
222Rn <0.3 µBq/m3 N2
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Mass spectrometer
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Techniques for analysis- Argon -
Rn analysis in the same way as for N2Same sensitivity can be achieved
Kr analysis difficult (contamination of massspectrometer with Ar)
Requires separation of Ar, Kr in advance (gas chromatography)Still some work to do…
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Which N2 is on the market?
0.06
0.04
0.3
40
Kr [ppt]
?
?
?
~50
222Rn[µBq/m3]
10Air Liquide (4.0)
0.0005Westfalen AG (6.0)
0.005SOL (6.0)
0.06Linde (7.0)
Ar [ppm]Company
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Which Ar is on the market?
Ar 6.0 means ∑(Contaminants) < 1 ppmBut noble gases are not includedN2, Ar produced in a similar way (rectification)
Reasonable to assume that Kr < 1ppm in Ar can be found on the market
Has to be proven ⇒ Technique for analysis
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Summary222Rn requirements similar to BOREXINOKr requirement in Ar ~1ppm
Adsorption techniques good for highest purities
Rn in N2 well under controlpurification as well as analysis
Will also work for Rn in Ar
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Summary
Purification of Ar from Kr not trivialRecently shown at MPI-K:
Purification of N2 from Kr by adsorption is possibleRequires gas phase and special adsorbersAr purification in the same way, but higher T (10 K)
Easiest approach: Buy pure enough N2, ArTo do: Development of technique for
measuring 1 ppm Kr in Ar