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1 s2.0 S0956053X97000214 Main
1 s2.0 S0956053X97000214 Main
1 s2.0 S0956053X97000214 Main
749-756, 1996
1997 Elsevier Science Ltd
All rights reserved. Printed in Great Britain
0956-053X/96 $15.00 + 0.00
Pergamon
PIh S0956-053X(97)00021-4
ORIGINAL CONTRIBUTION
L. C. Lange 1, C. D. Hills 2. a n d A. B. P o o l e 1
IGeomaterials Unit, Engineering Department, Queen Mary and WestfieM College, Mile End Road, London, U.K., E1 4NS
2Civil Engineering Department, Imperial College of Science, Technology and Medicine, Exhibition Road, London, U.K., SW7 2BU
ABSTRACT. This paper explores the kinetics of carbonation of cement-based solidified hazardous waste. This study is part
of a wide investigation into the effects of carbonation on solidified waste forms. Two commercially produced heavy metal
wastes were solidified with three different types of Portland cement and two mineral admixtures and carbonated under
controlled conditions. Measurements of the uptake of carbon dioxide were made for the different mixes and areas showing
the degree of carbonation for each cement system were defined. The effects of water/binder ratio, waste and binder type on
both total uptake of carbon dioxide and rate of carbonation were investigated and are discussed. 1997 Elsevier Science Ltd
INTRODUCTION
Cement-based solidification is frequently the technology of choice for immobilising soils and sludges
containing a variety of metal pollutants.~ This process is flexible, effective, accommodates complex
mixtures of contaminants and is economical enough
to be used for large volumes of waste. 2 Many workers 3-8 have tried to elucidate both individual and
synergistic effects of waste species on cement-based
binder systems in order to improve and extend the
solidification process. Nevertheless, at the present
time the mechanisms of fixation in operation during
the solidification/stabilisation are not completely
understood.
One phenomenon associated with Portland
cement-based materials that is receiving special
attention because of its potential effects on the properties of waste forms is atmospheric carbonation.
Through observations by our group and elsewhere it
has also been noticed that waste containing heavy
metals has an increased susceptibility to carbonation. 9,1 Most of the studies to date have concentra-
749
L. C. LANGE E T AL.
750
TABLE 1
P CxSHy+ (3-x)CaCO3
+ zCO2
:
~
C(x_z)SHy+ zCaCO3
Cements
OPC
WOPC
SRPC
Supplier
Blue circle
Blue circle
Blue circle
Phase
C3S %
C2S %
C3A %
C~,F %
CA %
Cl2A7%
C2A5%
Oxide
si02 %
A1203%
Fe203%
CaO %
Free Lime
MgO %
AlkaliEq.*
so3 %
IR*"
LOI'*
52
19
7
6
64
22
4.4
1.1
57
19
0
17
20.4
4.1
2.1
63.8
1.5
2.1
0.6
2.9
24.5
1.9
0.35
68.7
2.5
0.55
0.2
2.0
21.4
3.6
5.7
64
0.6
0.7
0.5
2.0
0.4
3.2
<0.1
1.0
0.6
1.5
Metals
Sr
Cr
Cu
Mn
Ni
Pb
Sb
Zn
Cd
Ba
As
Hg*
Waste 1
Waste 2
215
6638
8650
3137
4825
3265
1201
19,475
1025
575
7464
2514
175
11,275
175
1,675
312
288
25
410,000
ND
125
200
ND
Waates or Smld
10
OPC
WOPC
SRPC
PFA
GGBS
Waste 1
Waste 2
Water/binder (w/b) ratio
70
40
60
50
6O
~)
70
~)
80
B~ndecs
2O
10
20
30
~4)
50
60
70
80
90
Water
10
w/c ratio
0~0
40
2O
60
80
100
Time (rain.)
CO2 Uptake: WOPC and Waste 1
12
-- 10
8
w/c ratio = 0 . 2 0
L'-
2
0
20
40
60
0 = 1.0
80
100
Time (min.)
CO2 Uptake: SRPC and Waste 1
Composition r a n g e - - % (w/w)
5-80
5-80
5-80
15
40
10-80
10-80
0.07-3.0
50
TABLE 3
Range of Material Compositions in the Cement Solidified Wastes
Tested
Materials
8o
30
9o
20
8 2
RESULTS
751
12
10
8
~ 6
~ 4
o!
0
/
20
40
60
80
100
Time (rain.)
Binders are defined as cement only or cement + P F A or cement +
GGBS, P F A and GGBS were used at a fixed proportion of 15%
and 40%, respectively.
L . C . LANGE E T AL.
752
a) Control
b) OPC/admixtures/Waste1
Sand
Waste I
Generalarea
foundfor all
binders
37
7% 7X0
47
4\
70
P=<0.1%
[ ] OPC/WI HI=I0-15%
N~0
[ ] OPC/PFA/WIH2=8-11~
X 0 [ ] OPC/GGBS/W1H3=9-13eh
1V
20////
5y
AHI~
60"
~'-Y
Binders 10
20
I
30
40
c) OPC/admixtures/Waste2
50
70
80
90
Water Binders 10
Waste2
1
20////
20
30
40
d) WOPC/admixtures/WasteI
[ ] OPC/W2 HI =6-9%
[ ] OPC/PFA/W2H2 = 5-6%
x~0
50
60
10
20
30
40
50
90
Water
Waste I
3y
20
M__0A_4%
f~0
80
Xo
'
Binders
70
[ ] WOPC/WI HI =6-8%
[ ] WOPC/PFA/Wl H2 = 5 - 6%
~1 WOPC/GGBS/WI H3 = 6 - 8%
/ XO [] OPCIGGBSIw2H3~8-12%
4~30
N 10
60
X0
30
20
90/
X 0
707
.......X
60
70
80
90
Water
Binders
10
20
X
X,0
30
40
50
60
70
80
90
Water
FIGURE 3 (a--d). Ternary diagrams for the different waste/binder systems showing the effect of mix proportions on the degree of
carbonation.
Waste2
f) SRPC/admixtuccs/WastI
Waste 1
OFC/W2 HI = 3 5~:~
[]
70
[ ~ WOPC/PFAN2H2= 5 t)=/;
,X,~0
[ ] WOPC/GGBS/W2H~= ~ 7%
3O
753
SRPC/WI HI=6
1117~
~0
~0
30~M=0,=, 1 - .5 c/~
[]
SRPC/GGBS/WI H3=6-7rz ,
~ / ~
40
5(1
50
60/
,,,u~/
5~4 o
70 6 6 0 ~ ~
P=<0.1 ~
30
P=<0. 1%
30
2O
~/
"J
/ '/
\
20
30
40
50
60
70
Note: The area of WOPC/GGBS is overlapped by WOPC only
Binders
10
80
90
Water
g) SRPC/admixtures/Waste 2
Binders 10
20
30
40
50
60
70
Note: The SRPC only area is partially overlapped by SRPC/GGBS
80
90
Water
Waste 2
5O
Binders
10
20
30
40
50
60
70
80
90
Water
FIGURE 3 (e--g). Ternary diagrams for the different waste/binder systems showing the effect of mix proportions on the degree of
carbonation.
DISCUSSION
The influence of binder choice on the carbonation of
cement-solidified wastes has been investigated and
detailed in this work. It has been established that if
samples are highly carbonated (see optimised mix
designs in Fig. 3), they will have enhanced physical
and chemical properties when compared to nonoptimised samples, z3 Carbonation was strongly influenced by the complexity of industrial wastes, type of
cement/admixture and w/b ratio, supporting the premise that these factors determine the effective diffusivity of carbon dioxide within a waste/binder system.
L . C . L A N G E ET AL
754
_oo
Sand/OPC
14
'~
Systems
4a
10
I w/b=o.o9
w/b = 0.33
w/b=0.5
Waste I /OPC
14" 4b
0 !
OPC
'
OPC/PFA
[I
"~
~ 10"
4c
OPC
I~
OPC/PFA
OPC/GGBS
Systems
4d
J
12-
w/b = 0.33
i~I
,.~ = o.5
~.~
6-
~5~~,~
4-
] woo = 0.09
w/b = 0.20
] w/b = 0.33
w/b = 0.5
w/b = 1.0
10.
-~
8-
14.
~=o.2o
~0 ~
"
Sand / WOPC
I w/b = 0.09
12 ~
w/b = 0.33
w/b=0.5
6'
'-I w/b=0.09
O-
OPC/GGBS
oo.
Systems
8.
6.
4.
20
OPC
OPC/PFA
Waste I /WOPC
14
4e
OPC/GGBS
Systems
10
8
O
r..)
WOPC
WOPC/PFA
Waste 2/WOPC
41
[ w/b : 0.09
w/b = 0.20
w/b = 0.33
w/b = 0.5
w/b : 1.0
12
0.
4f
12
10
WOPC/GGBS
Systems
] w/b = 0.09
w/b = 0.20
w/b = 0.33
w/b = 0.5
6
4
2o
WOPC
WOPC/PFA
WOPC/GGBS
0~
WOPC
WOPC/PFA
Waste I /SRPC
WOPC/GGBS
Systems
1
14- 4g
[
[-'--7
"~ 1o;
w / b = 0.20
141
w / b = 0.33
w / b = 0.5
10
I w / b = 0.09
12-'
w / b = 1.0
O
~s
6-
4h
] w,'b=0.09 I
12
w/b = 0.33 I
w.:_o: /
8-t
67
4-
:1
2SRPC
SRPC/PFA
SRPC/GGBS
SRPC
SRPC/PFA
,,, 12
o
10
~.
I w/b = 0.09
w/b = 0.20
w/b = 0.33
w/b = 0.5
w/b = 1.0
2
SRPC
FIGURE
SRPC/PFA
SRPC/GGBS
4. T o t a l c a r b o n d i o x i d e u p t a k e a f t e r 100 m i n f o r s e l e c t e d m i x e s o f d i f f e r e n t w / b r a t i o .
SRPC/GGBS
microstructural changes in the silica gel phase (topochemical precipitation of gel). Some authors have
shown that the microporosity (gel pores) inside the
reaction product (silica-gel) is enhanced by the presence of CO2 ,28 GGBS/cement pastes contain less
calcium hydroxide than Portland cement and consequently a reaction between CSH and CO2 may
become more pronounced. As more CSH becomes
involved in the carbonation process, precipitation of
calcium carbonate results, accompanied by a sharper
decrease.
Moisture Content
The amount of water in the waste/binder system is
crucial for carbonation to proceed at an optimum
rate. Water is necessary for a reaction with CO2, but
too much water severely limits the rate of the reaction. In other words, as the pores are filled with
water, the penetration of carbon dioxide is hindered
as the rate of diffusion of COz is reduced; if on the
other hand pores are completely dry, the reaction of
CO2 is absent. Therefore, this implies that solvation
of carbon dioxide is critical for effective carbonation
to proceed. It is also shown that different water contents are required for different cement types and
might in return be related to the specific surface area
of individual cements. Figure 2 illustrates these
effects by showing the increased delay in induction
time in the carbonation reaction as water content
increases.
3.
4.
5.
6.
7.
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9.
10.
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12.
13.
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20.
21.
22.
23.
24.
25.
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