Studies of milling technology's approaches for ...ย ยท โกSpecific surface area measurement by NMR R...
Transcript of Studies of milling technology's approaches for ...ย ยท โกSpecific surface area measurement by NMR R...
Studies of milling technology's approaches for establishing
the chemical recycles on some wasted glasses.
โMasataka KAMITANI1)2), Mitsunori KONDO1), Atsushi NAKAHIRA2)
1)Makino corporation (Aichi Tokoname,Japan)
2)Graduated School of Osaka Prefecture University.(Osaka Sakai,Japan)
Japan-Korea powder technology symposium 2015
Hold on Soul National University Sept.14,2015
๏ผ๏ผSome directions for wasted glass chemical recycle applications
โ Silicate resources for minerals and ceramics synthesis
โกIon exchanging devices for environmental cleanup
โขThe dehydration condensation for like cement
Synthesized LTA in Bamboo inside pore
200nm
Condensed mass from LCDG
200ฮผm
Abstracts of Spring Meeting of Japan Society of Powder and Powder Metallurgy,2013
Abstracts of Autumn Meeting of Japan Society of Powder and Powder Metallurgy,2013
IREP the first Meeting in Imabari,2013
2nd meeting on Environmental radioactive decontamination technology, Tokyo 2013
Materials Science Forum Vols,22-227 (1996) pp.587-592
Kinzoku,Vol.68 (1998) No.9
LTA
M.kamitani,A,Nakahira,T.Wakihara๏ฝคet.al ISAC-5,Wuhan,Chaina 2014
M.Kamitani,M.Kondo.A.Nakahira, J. Jpn. Soc. Powder Powder Metallurgy Vol. 62, No. 6 ,2015
Fabrication and evaluation of hybrid materials from A-zeolite and ground glass powders for vitrified
radioactive, j. ceram. soc, japan 122 (2) 151-155,2014
M.kamitani,A,Nakahira,T.Wakihara๏ฝคet.al ISAC-5,Wuhan,Chaina 2014
Abstracts of Autum Meeting of Japan Society of Powder and Powder Metallurgy,2014
3. Fundamental procedure of chemically activation for wasted glass by Ball milling
Energy consumption of milling with ball media
compressive impact shear
โง
Fracture mode of glass grain by impact
Rumpf, H, Struktur der Zerkleinerungswissenschaft
Aufbereitungs-Technik No. 8/1966 421-435
Fig.1 model of generating forces in ball mill
ref.
Fig.2 fracture model from reference
Optimization of ball milling condition by DEM simulation
j-th ball
i-th ball
usus
s
Ks
slider
i-th ballunun
n Kn
j-th ball
Normal force Shear force
j-th ball
i-th ball
usus
s
Ks
slider
i-th ballunun
n Kn
j-th ball
Normal force Shear force
Ball weight
Impact speed
Specimen weight
Number of impact
Fig.3 DEM simulation based on Voigt model
Mill dimension
L=725mm diameter=725mm
Ball: ฯ๏ผ10-30mm steal
0.75 0.80 0.85 0.90 0.95
2500
3000
3500
4000
4500
5000
Impa
ct
energ
y (J
/s)
Relative rotational speed, N/Nc (-)
J=40 J=50 J=60
dB=10 mm
0.75 0.80 0.85 0.90 0.95
2500
3000
3500
4000
4500
5000
Impact
energ
y (
J/s)
Relative rotational speed, N/Nc (-)
J=40 J=50 J=60
dB=15 mm
0.75 0.80 0.85 0.90 0.95
2500
3000
3500
4000
4500
5000
Impact
energ
y (
J/s)
Relative rotational speed, N/Nc (-)
J=40 J=50 J=60
dB=30 mm
Fig.4 Impact energy estimation by
DEM simulation.
This point
Energy consumption
Mill dimension
L=725mm diameter=725mm
Ball filling ratio=0.5
Ball: ฯ๏ผ15mm steal
Raw material:24-32Kg
8
โ
โก
โข
Glass weight
๏ผkg๏ผ
Ball milling condition
rotation Ball radius occupy
sampling๏ผ๏ฝ๏ฝ๏ผ
0.5 1 2 3 6
0.95
0.95
32
32
24
0.85
15
15
15
50
50
50
๏ผN/Nc) (mm๏ผ ๏ผ๏ผ ๏ผ
โ
โ
โ โ โ โ
โ โ โ ใผ ใผ
ใผ โ โ ใผ
๏ผฎ๏ฝ๏ผ Glass species
LCDG1)
โฃ
โค
SLG2) 0.95 20
15
30
30 0.95
50
50
โ โ โ โ โ
โ โ โ โ โ
ใผ
ใผ
ใผ
โ
โ
๏ผด๏ฝ๏ฝ๏ฝ๏ฝ .๏ผ Test plan
1๏ผโ โกโข๏ผLCDG alumino-silicate glass๏ผ๏ผณ๏ฝ๏ผฏ๏ผ/๏ผก๏ฝ๏ผ๏ผฏ๏ผ/๏ผฃ๏ฝ๏ผฏ/๏ผฎ๏ฝ๏ผ๏ผฏ๏ผ58.8/17.1/9.5/0.3(๏ฝ๏ฝ๏ผ ratio๏ผ
2๏ผโฃโค๏ผSoda-Lime Glass๏ผ๏ผณ๏ฝ๏ผฏ๏ผ/๏ผฃ๏ฝ๏ผฏ/๏ผฎ๏ฝ๏ผ๏ผฏ๏ผ73/5/17๏ผ๏ฝ๏ฝ๏ผ ratio๏ผ
4.Experiment and Results
โฅ3) 12 0.75 15
50 ใผ โ โ โ โ โ
3) Test โฅ is another experiment for in-line measuring system development.
Milling by small 50L mill on another glass:๏ผณ๏ฝ๏ผฏ๏ผ/๏ผก๏ฝ๏ผ๏ผฏ๏ผ/Mg๏ผฏ/๏ผฎ๏ฝ๏ผ๏ผฏ๏ผ60.2/15.2/7.2/16.8(๏ฝ๏ฝ๏ผ ๏ผ
Al2O3
โ Milling test plan
2hr
3hr
2hr
4hr
5hr 6hr
6hr
Fre
qu
en
cy
Testโก Testโก
Fig. 5 Grain size distribution of test2 and test5 by Laser diffraction MT-3000โ ก
โกGrain size distribution change
6hr
2hr
6hr 4hr
6hr
2hr 6hr
5hr
T-2
T-5
(ฮผm) (ฮผm)
(ฮผm) (ฮผm)
Fre
qu
nc
y (
vo
l.ba
sis)
Fre
qu
nc
y (
vo
l.ba
sis)
Cu
mu
lativ
e(%
) C
um
ula
tiv
e(%
)
5hr
3hr
4hr
โขMorphology on SEMโs images
Fig.8 SEMโs images of T-2 and T-5 samples that 6hr milled.
Raw material
T-2
T-5 T-5
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
0 1 2 3 4 5 6 7 8 9
Sp
ec
ific
su
rfa
ce
are
a (
m2/g
)
Milling time (hr)
LCDG(T-2)
SLG(T-5)
โฃSpecific surface area
Fig.9 BET specific surface area of T-2 and T-5 measured by Bellsorp mini โ ก.
0
0.2
0.4
0.6
0.8
1
0 0.1 0.2 0.3 0.4 0.5 0.60
0.2
0.4
0.6
0.8
1
0 0.1 0.2 0.3 0.4 0.5 0.6Atomic distance (nm)
Exis
ten
ce
ra
tio
Atomic distance (nm)
โคXAFS analysis
T-2:LCDG T-5:SLG
Fig.10 XAFS profiles of T-2 and T-5
6hr
raw 2hr
6hr
raw
2hr
The monochromator serves soft X-rays in the
energy region from 585 to 4000 eV
KTP (KTiOPO4)
Si-K
Soft X-Ray Beamline for Photoabsorption Spectroscop
Thanks UVSOR
6hr
Fig.11 Titration curves of T-2 and T-5 samples. Solid concentration is 10% ๏ผN-NaOH used
โฅTitration for surface analysis
Measured by DT-1200
1N-
NaOH
blank
1.54 1.25
BET 2.8m2/g
BET 2.1m2/g
BET
1.8m2/g
2hr
4hr
6hr
blank
4.93
T-2
T-5
6hr
5hr
2hr
3hr
Zero-charge point
4hr
3hr 6hr 12hr
Test2-6hrmilling reacted in S-solution for 3-12hr at 95โ
Fig.12 SEMโs images of autoclaved grains
5. For Silica resource
LTA
0
10000
20000
30000
40000
50000
60000
0 10 20 30 40 50
0
5000
10000
15000
20000
25000
0 10 20 30 40 50
0
5000
10000
15000
20000
25000
30000
0 10 20 30 40 500
5000
10000
15000
20000
25000
30000
35000
40000
45000
0 10 20 30 40 50
T-2-3hr milling
T-2-6hr milling
3hr reaction 6hr reaction 12hr reaction
6hr reaction 12hr reaction
Fig.13 XRD profiles of autoclaved sample
0
10000
20000
30000
40000
50000
60000
70000
80000
0 10 20 30 40 50
2ฮธ(degree) 2ฮธ(degree)
2ฮธ(degree)
2ฮธ(degree)
2ฮธ(degree)
Inte
nsi
ty (
cp
s)
Inte
nsi
ty (
cp
s)
Inte
nsi
ty (
cp
s)
Inte
nsi
ty (
cp
s)
Inte
nsi
ty (
cp
s)
0
0.015
0.03
0.045
1 10 100 1000
BJH-Plot
dp/nm
dVp/
dlogd
p
โ aqueous washing treatment
T-2 6hr milled
Washed by water
Fig.14 BJH profiles of T-5-6hr milling samples that washed by pure water.
6. For Ion exchange device
BET=2.8m2/g
BET=9.6m2/g
NaI detector (NHC-7 fuji electric)
Sample in U8 cantor Pb shielding brock
โกDecomtanimation of radio active material;137Cs
โTesting solution
Fig.15 photos and schematic view of radioactive Cs removing test.
Wash out solution from sewage ashes in Fukushima pref.
134Cs: 213ยฑ7.5 (Bq/kg)
137Cs: 383ยฑ14
Ge detector model GC-3020,canberra
(Bq/kg)
Concentrate to
around 137Cs:1200Bq/kg
material w/s shaking
time(min)
137Cs initial (Bq/kg)
137Cs remain
(Bq/Kg) removing(%)
washed milling Glass
powder T-2-6hr&washed
10 10 1262 902 18.9
fine Mordenite
10
10
1262
382.9 69.6
coarse Mordenite 10 786 37.7
A-type Zeolite 10 1219 3.3
Table.3 Test result of removing 137Cs
6hr milled LCD glass(30g)
10N NaOH 30ml
RT one night
Hardened sample
Casting
Mixing
7. For Dehydration Condensation
โ Hardening procedure
0
10
20
30
40
50
60
70
80
90
100
05001000150020002500300035004000
Tra
nsm
itta
nc
e(%
)
wavenumber(cm-1)
O-H Stretching
Si-O Stretching
Si-O Rocking
Si-O Bending
H-O-H Bending
6hr
milled
hardened
Fig.18 FT-IR spectrums of samples
โฃ Chemical bonding
8. Inline measuring for ball milling
-0.20
0.00
0.20
0.40
0.60
0.80
0
0.5
1
1.5
2
2.5
0 5 10
dS/d
t
BET
(m2/g
)
-30
-20
-10
0
0 5 10
Ze
ta p
ote
ntia
l
(mV
)
-10
-5
0
5
10
30
40
50
60
70
0 5 10
Si c
on
ce
ntr
ate
ra
te
(mg
/Lใป
hr)
Si c
on
ce
ntr
atio
n
(pp
m)
Flocks and
agglomerates
Agglomerates
scrap and build
Fine milling
1st St. (Start๏ฝ4hr)
2nd St.(4๏ฝ8hr)
Agglomerates
crush and formed
Particles down sizing
and agglomerates
formation
โ The model of glass milling from T-โฅ
โกSpecific surface area measurement by NMR
Rav:reciprocal of sample relaxation time
Rav=ัฑ๐๐๐ฟ๐๐ ๐ ๐ โ ๐ ๐ +Rb
=KASัฑp๏ผRb
ัฐp๏ผvolume fraction of particles
S๏ผsurface area
Rs:reciprocal of adsorption relax.time
R๏ฝ:reciprocal of solvent
KA: coefficient of wettability
=R
av๏ฝฐR
b
๐ ๐
Rsp
Pulse NMR
0
500
1000
0 1000 2000 3000
Ma
gn
etiza
tio
n
Time [milliseconds]
0.3T
T2 mode:Spin-Spin relaxation
A short RF Pulse B1
Rotates H atoms
N
S
N S
N S
N
S
N
S
N
S
-> Bo
->
Bo
B1 Temporary
magnetic field
When B1 disappears, H atoms realign with Bo
producing a signal
โขComparison with BET and R2sp
0
0.5
1
1.5
2
2.5
0 2 4 6 8 10
BE
T s
pec
ific
su
rfac
e (m
2/g
)
Milling time(hr)
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
5
0 2 4 6 8 10
Ca
lcu
late
d s
pe
cific
su
rfa
ce
are
a f
rom
R2
sp (
m2/g
)
Milling time (hr)
0
20
40
60
80
100
120
140
160
180
200
0 500 1000 1500 2000
Relaxation time (ms)
Fig.20 The relaxation time curves on T-โฅ
Fig.21 Comparison with cal.surface area and BET
1hr
2hr
3hr
4hr 6hr
9. Summery of this presentation
๏ผ๏ผWeโve confirmed structural changes of wasted glass materials by ball milling.
๏ผ๏ผBy ball milling , the higher impact energy makes disorder on grain surface or inner
structure, We consider they play as dissolving points, and/or to be meso scale
cavities on grain surface.
It is very important knowledge for the chemical recycling technology.
๏ผ๏ผWe would develop the operating methods for environmental cleanup with
these devices
3) Weโve recognized these phenomenon induced by โMechanochemical effectโ
5๏ผWeโve already developed the optimized milling systems on inline surface area
that mainly consists with P-NMR. measuring