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PPP 0024
ABSTRACI-
APPLICATIONS OF GEOPOLYMER TECHNOLOGY
TO WASTE STABILIZATION
Douglas C. Comrie
John H. Paterson
Douglas J. Ritcey
D. C o d e Consulting Ltd.
120 Traders Boulevard East
Suite 209
Mississauga, Ontario
L4Z 2H7
Hazardous wastes can be rendered innocuous
through chemical (waste stabilization) or
physical (waste encapsulation) methods. A
research program has been conducted at D.
C o d e Consulting Ltd. in order to evaluate
geopolymer as an agent for both waste
stabilization and encapsulation.
Physical properties of solidified waste and sand
mortar mixes have been examined on the basis
of compressive strength testing. Abilities of
geopolymer to render waste chemically
innocuous have been assessed on the basis of
leachate testing carried out in accordance with
Ontario’s Ministry of Environment Regulation
309 guidelines.
Preliminary results show this inorganic binder
as extremely effective in reducing metal
leachability in a wide range of wastes, and that
the physical properties of solidified products
make it an ideal candidate for waste
stabilization or encapsulation.
INTRODUCTION
Waste treatment can be effected through both
physical and chemical processes. Waste
treatment and stabilization may be carried out
either independent of, or in conjunction with
physical encapsulation. While chemical
treatment may render the waste itself essentially
chemically inert and no longer susceptible to
releasing toxins in response to leaching, physical
encapsulation concentrates on isolating the
waste from interaction with surrounding surface
and groundwater.
There are many stabilization agents available
for the treatment of toxic waste. Testing of
these materials has met with varying degrees of
success at reducing the leachability of
contaminants in the waste. The purpose of this
research program was to evaluate the
performance of one such stabilization agent - an
inorganic binder known as geopolymer.
161
GEOPOLYMERS PHYSICAL CHARACTERISTICS
Geopolymers are inorganic binders consisting
of two components: a very fine and dry
powder, and a syropy, highly alkaline liquid.
Liquid and powder portions are combined to
produce a mixture of molasses-like consistency
which is then reacted with the desired waste or
aggregate. Blending of the two binder
components can be readily carried out with the
aid of conventional cement mixing technology.
The resulting waste-binder mixture can be
poured into molds (for example, fibre drums
such as might be obtained from a concrete
products supplier); drier mixes have potential
for extrusion.
The geopolymeric reaction occurs as a result of
reacting alumino-silicate oxides with alkali
(NaOH, KOH) and soluble alkali polysilicates.
Resulting from this reaction is the formation of
SiO, and A10, tetrahedra linked by shared
oxygens. A mildly exothermic reaction in the
alkali activated mixture is accompanied by
hardening and polycondensation.
The basis of the sialate (or, silicon-oxo-
aluminate) network of SiO, and A10,
Figure 1: NO, and SO, tetrahedra - basis
of the sialate network.
tetrahedra is illustrated in Figure 1. Positive
ions, such as sodium, potassium, lithium,
calcium or barium, must be present in the
framework cavities in order to achieve charge
balance.
Geopolymers are characterized by a number of
interesting physical characteristics, including
thermal stability, high surface smoothness,
precise moldability and hard surfaces (4-7 on
Moh's scale) (Davidovits and Davidovits, 1987).
These properties are commonly imparted to
products created through a combination of
binder with waste materials. In terms of waste
stabilization or encapsulation, the most
significant physical property imparted by
geopolymers is their ability to transform soft,
disaggregated or sludge-like wastes into hard,
cohesive solids in remarkably short time frames.
Physical testing has been carried out on
unconfined cubes created from mortar mixes of
sand and geopolymer. Compressive strengths of
40 MPa have been achieved over a 28 day cure
period; strengths of 30 MPa (75% of final
strength) are acquired in the initial two days of
curing (Figure 2). Strengths are acquired with
considerable speed in comparison to mortars
developed fromregular Portland cement (Figure
3).
A Irj
n
g"
4P
5
u)
f
8
-
o z 4 o a 1 0 1 ~ 1 4 1 e 1 a z u n n t e a a
GeopoIymer Content (Percent1
..igure 2: Comparison of 2 and 28 day
strengths in inorganic binder
based mortars.
163
Setting Time (Hours)
Figure 3: Comparison of Norma
Portland and InorganicBinder
Based Concrete Initial
Strengths.
In fact, some inorganic binders have been
developed to form solid, cohesive masseswithin
one to two minutes of mixing with aggregate or
waste forms. Of course, compressive strengths
achieved depend on the nature of the aggregate
or waste form employed in conjunction with the
binder, and the amount of binder used.
CHEMICAL CHARACIERISTICS
In addition to their physical properties,
geopolymers are characterized by an ability to
resist chemical attack. This is attributed to the
fact that, unlike cements, lime does not play a
part in the lattice structure which provides the
structural strength to the product. The
resistance provided against chemical attack is
best illustrated by the ability of geopolymer to
retain toxins during acidic leaching.
In order to examine this property, a variety of
toxic waste samples have been collected from
different waste generators. Each sample was
split into three and the first portion was
assayed for metal concentrations. The second
portion was subjected to leachate testing in
accordance with Ontario’s Ministry of the
Environment Regulation 309, Schedule 4
guidelines, calling for pulverization of the
sample followed by tumbling in acetic acid. The
third portion of each waste was treated with
geopolymer and, after curing for 7 days, leach
tested. Results were compared with the
maximum permissible leachate concentrations
allowed by the Ministry of Environment.
Tests conducted on waste at a southern Ontario
scrap yard have proved most successful.
Bulldozer and soil movement operations at the
scrap yard, which has been used for crushing
and compacting both automotive and industrial
scrap, have resulted in contamination which
extends approximately 2 meters down into the
soil. Of prime concern is lead contamination,
resulting from scrapped car batteries. Analysis
of soil from the yard indicates lead
concentrations in the order of 6,000 ppm, with
25.3 mg/l leaching out during Regulation 309
style tests. In contrast, samples treated with a
geopolymeric inorganic binder leached out only
2.1 mg/l, well below the Ministry of
Environment limit for safe emissions of 5 mg/l.
I A
v / c-
Figure 4: ~ Comparison of Leachate Quality
in Treated and Untreated Scrap
Yard Waste.
Similar tests were conducted on contaminated
soils surrounding a southern Ontario refining
and smelting operation. A series of leaks and
spills during the plant’s forty year operational
life have resulted in lead contamination to a
1 h?
depth of three meters. Concentrations of lead
in the soil average about 285,000ppm, with 204
mg/l released to leachate during Regulation
309 style leaching. Geopolymerization brings
this level down by an order of magnitude, to
18.3 mg/l.
Figure 5 illustrates the effect on leachate
quality as a result of increasing geopolymer
content. Ore processing waste (tailings) from
an Ontario base metal mining operation was
solidified with 10, 15 and 25 weight percent
geopolymer.
:&re 5: Comparisonof VuLossDuring
Leaching -Mine Tailingswith
lo%, 15% and 15% Binder.
WASTE TREATMENT APPLICATlONS
The physical and chemical properties of
geopolymers and of products created with
geopolymers makes them attractive candidates
for a variety of waste stabilization and
encapsulation situations (Comrie, 1988;
Comrie and Davidovits, 1988; Davidovits and
Comrie, 1988). The automotive scrap yard and
the refining and smelting operation noted
above represent good examples of possible
applications.
Work has already been initiated at the
automotive scrap yard on a pilot plant (20
tonne) scale, and contaminated soil has been
screened to remove inordinately coarse material
which might interfere with the blending
equipment. Mixing will be carried out using
conventional concrete mixing technology, and
the resulting inorganicallybound mixture will be
poured into fibre barrels. After a short curing
time, this solidified and stabilized waste can
then be transported to a non-hazardous landfill
site, at considerable cost savings over disposal at
a hazardous waste facility. This alternative is
made possible by the fact that solidificationwith
geopolymer reduces leachate levels to
concentrations significantly below those.
considered hazardous by the Ministry of
Environment in Ontario.
Plans for remediation of the refining and
smelting site noted above call for a combination
of chemical waste stabilization and waste
encapsulation. The most contaminated area on
the site will be excavated to create an empty
"vault", with the removed soil stored nearby.
While the vault is lined with low permeability,
high strength geopolymer concrete, the soil set
aside will be treated with geopolymer to create
a solid of minimal leachate hazard. The treated
soil will then be returned to the vault and
capped with 100 mm of geopolymer concrete,
on top of which will be placed an additional 600
mm of top soil. The entire perimeter of the
vault will be surrounded with peripheral surface
water ditches, resulting in a waste management
unit which contains a waste of minimal
reactivity and which is isolated from interaction
Topaail
Low pennwbfllty llnr
~~
Figure 6: Cross-section of Waste
ManagementUnitforTreatment
of Smelter Yard Waste.
with ground and surface water (Figure 6).
The unique properties of geopolymer and
inorganic binders, including rapid achievement
of high strengths and the ability to immobilize
chemical toxins even under conditions of acidic
leaching, should result in some interesting
future applications.
REFERENCES
COMRIE, D.C. (1988):
New Hope for Toxic Waste, IN: The World & I,
August, 1988,Publ. Washington Times, pp.171-177.
COMRIE, D.C. and DAVIDOVITS, J.(1988):
Waste Containment Technology for Management of
Uranium Mill Tailings. Presented at the 117th
Annual Meeting of the AIMEISME, January, 1988,
Phoenix, Arizona.
REFERENCES (continued)
DAVIDOVITS, J. and COMRIE, D.C.(1988):
Archaeological Long-Term Durability: of Hazardous
Waste Disposal - Preliminary Results with Geopolymer
Technologies. Div. Env. Chemistry, American Chemical
Society,Toronto, June, 1988. Preprint.
DAVIDOVITS, J. and COMRIE, D.C. (1989):
Applications of Geopolymeric Grouts in the Prevention
of Environmental Contamination. American Chemical
Institute National Convention, Atlanta, February, 1989.
Preprint.
DAVIDOVITS, J. and DAVIDOVITS, M.(1987):
Geopolymer Poly(sialate)/Poly(sialate-siloxo) Mineral
Matrices for Composite Materials. Proc. VIth
International Conference on Composite Materials,
Imperial College, London, UK, July 20-24, 1987.
Preprint.
Synthesis of new high-temperature Geopolymers for
reinforced plastics and composites, SPE PACTEC '79,
Costa Mesa, California, Society of Plastics Engineers,
USA, 1979, pp. 151-154.
Disclaimer
The work described in this paper w a s
not funded by the U.S. Environmental
Protection Agency. The contents do
not necessarily reflect the views of
the Agency and no official endorse-
ment should be inferred.
Cement casting and sintering are two treatment
techniques for hazar g toxic metals. Research in the
wastes. Treatability
arsenic-bearing soils nt at the Whitmoyer Laboratories
Superfund Site.
Treatability study
Cement casting was
waste combination pri effective in promoting waste
stabilization.
successful in stabilizing
the calcium-arsenic ot effective on the iron-
quantities of arsenic
aINTRODUCTION
The Whitdyer Laborat ries
s located in Ja kson
Veterihary
C o u b t y ,
arsenic! precipitation in an unhined
lagoon. When environmeptal
conseqdences from this practice were
noted: the sludge was excavated and

The site operator condbcted a
groundwater pump-and-treat program at
166

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Applications of geopolymer technology to waste stabilization

  • 1. PPP 0024 ABSTRACI- APPLICATIONS OF GEOPOLYMER TECHNOLOGY TO WASTE STABILIZATION Douglas C. Comrie John H. Paterson Douglas J. Ritcey D. C o d e Consulting Ltd. 120 Traders Boulevard East Suite 209 Mississauga, Ontario L4Z 2H7 Hazardous wastes can be rendered innocuous through chemical (waste stabilization) or physical (waste encapsulation) methods. A research program has been conducted at D. C o d e Consulting Ltd. in order to evaluate geopolymer as an agent for both waste stabilization and encapsulation. Physical properties of solidified waste and sand mortar mixes have been examined on the basis of compressive strength testing. Abilities of geopolymer to render waste chemically innocuous have been assessed on the basis of leachate testing carried out in accordance with Ontario’s Ministry of Environment Regulation 309 guidelines. Preliminary results show this inorganic binder as extremely effective in reducing metal leachability in a wide range of wastes, and that the physical properties of solidified products make it an ideal candidate for waste stabilization or encapsulation. INTRODUCTION Waste treatment can be effected through both physical and chemical processes. Waste treatment and stabilization may be carried out either independent of, or in conjunction with physical encapsulation. While chemical treatment may render the waste itself essentially chemically inert and no longer susceptible to releasing toxins in response to leaching, physical encapsulation concentrates on isolating the waste from interaction with surrounding surface and groundwater. There are many stabilization agents available for the treatment of toxic waste. Testing of these materials has met with varying degrees of success at reducing the leachability of contaminants in the waste. The purpose of this research program was to evaluate the performance of one such stabilization agent - an inorganic binder known as geopolymer. 161
  • 2. GEOPOLYMERS PHYSICAL CHARACTERISTICS Geopolymers are inorganic binders consisting of two components: a very fine and dry powder, and a syropy, highly alkaline liquid. Liquid and powder portions are combined to produce a mixture of molasses-like consistency which is then reacted with the desired waste or aggregate. Blending of the two binder components can be readily carried out with the aid of conventional cement mixing technology. The resulting waste-binder mixture can be poured into molds (for example, fibre drums such as might be obtained from a concrete products supplier); drier mixes have potential for extrusion. The geopolymeric reaction occurs as a result of reacting alumino-silicate oxides with alkali (NaOH, KOH) and soluble alkali polysilicates. Resulting from this reaction is the formation of SiO, and A10, tetrahedra linked by shared oxygens. A mildly exothermic reaction in the alkali activated mixture is accompanied by hardening and polycondensation. The basis of the sialate (or, silicon-oxo- aluminate) network of SiO, and A10, Figure 1: NO, and SO, tetrahedra - basis of the sialate network. tetrahedra is illustrated in Figure 1. Positive ions, such as sodium, potassium, lithium, calcium or barium, must be present in the framework cavities in order to achieve charge balance. Geopolymers are characterized by a number of interesting physical characteristics, including thermal stability, high surface smoothness, precise moldability and hard surfaces (4-7 on Moh's scale) (Davidovits and Davidovits, 1987). These properties are commonly imparted to products created through a combination of binder with waste materials. In terms of waste stabilization or encapsulation, the most significant physical property imparted by geopolymers is their ability to transform soft, disaggregated or sludge-like wastes into hard, cohesive solids in remarkably short time frames. Physical testing has been carried out on unconfined cubes created from mortar mixes of sand and geopolymer. Compressive strengths of 40 MPa have been achieved over a 28 day cure period; strengths of 30 MPa (75% of final strength) are acquired in the initial two days of curing (Figure 2). Strengths are acquired with considerable speed in comparison to mortars developed fromregular Portland cement (Figure 3). A Irj n g" 4P 5 u) f 8 - o z 4 o a 1 0 1 ~ 1 4 1 e 1 a z u n n t e a a GeopoIymer Content (Percent1 ..igure 2: Comparison of 2 and 28 day strengths in inorganic binder based mortars. 163
  • 3. Setting Time (Hours) Figure 3: Comparison of Norma Portland and InorganicBinder Based Concrete Initial Strengths. In fact, some inorganic binders have been developed to form solid, cohesive masseswithin one to two minutes of mixing with aggregate or waste forms. Of course, compressive strengths achieved depend on the nature of the aggregate or waste form employed in conjunction with the binder, and the amount of binder used. CHEMICAL CHARACIERISTICS In addition to their physical properties, geopolymers are characterized by an ability to resist chemical attack. This is attributed to the fact that, unlike cements, lime does not play a part in the lattice structure which provides the structural strength to the product. The resistance provided against chemical attack is best illustrated by the ability of geopolymer to retain toxins during acidic leaching. In order to examine this property, a variety of toxic waste samples have been collected from different waste generators. Each sample was split into three and the first portion was assayed for metal concentrations. The second portion was subjected to leachate testing in accordance with Ontario’s Ministry of the Environment Regulation 309, Schedule 4 guidelines, calling for pulverization of the sample followed by tumbling in acetic acid. The third portion of each waste was treated with geopolymer and, after curing for 7 days, leach tested. Results were compared with the maximum permissible leachate concentrations allowed by the Ministry of Environment. Tests conducted on waste at a southern Ontario scrap yard have proved most successful. Bulldozer and soil movement operations at the scrap yard, which has been used for crushing and compacting both automotive and industrial scrap, have resulted in contamination which extends approximately 2 meters down into the soil. Of prime concern is lead contamination, resulting from scrapped car batteries. Analysis of soil from the yard indicates lead concentrations in the order of 6,000 ppm, with 25.3 mg/l leaching out during Regulation 309 style tests. In contrast, samples treated with a geopolymeric inorganic binder leached out only 2.1 mg/l, well below the Ministry of Environment limit for safe emissions of 5 mg/l. I A v / c- Figure 4: ~ Comparison of Leachate Quality in Treated and Untreated Scrap Yard Waste. Similar tests were conducted on contaminated soils surrounding a southern Ontario refining and smelting operation. A series of leaks and spills during the plant’s forty year operational life have resulted in lead contamination to a 1 h?
  • 4. depth of three meters. Concentrations of lead in the soil average about 285,000ppm, with 204 mg/l released to leachate during Regulation 309 style leaching. Geopolymerization brings this level down by an order of magnitude, to 18.3 mg/l. Figure 5 illustrates the effect on leachate quality as a result of increasing geopolymer content. Ore processing waste (tailings) from an Ontario base metal mining operation was solidified with 10, 15 and 25 weight percent geopolymer. :&re 5: Comparisonof VuLossDuring Leaching -Mine Tailingswith lo%, 15% and 15% Binder. WASTE TREATMENT APPLICATlONS The physical and chemical properties of geopolymers and of products created with geopolymers makes them attractive candidates for a variety of waste stabilization and encapsulation situations (Comrie, 1988; Comrie and Davidovits, 1988; Davidovits and Comrie, 1988). The automotive scrap yard and the refining and smelting operation noted above represent good examples of possible applications. Work has already been initiated at the automotive scrap yard on a pilot plant (20 tonne) scale, and contaminated soil has been screened to remove inordinately coarse material which might interfere with the blending equipment. Mixing will be carried out using conventional concrete mixing technology, and the resulting inorganicallybound mixture will be poured into fibre barrels. After a short curing time, this solidified and stabilized waste can then be transported to a non-hazardous landfill site, at considerable cost savings over disposal at a hazardous waste facility. This alternative is made possible by the fact that solidificationwith geopolymer reduces leachate levels to concentrations significantly below those. considered hazardous by the Ministry of Environment in Ontario. Plans for remediation of the refining and smelting site noted above call for a combination of chemical waste stabilization and waste encapsulation. The most contaminated area on the site will be excavated to create an empty "vault", with the removed soil stored nearby. While the vault is lined with low permeability, high strength geopolymer concrete, the soil set aside will be treated with geopolymer to create a solid of minimal leachate hazard. The treated soil will then be returned to the vault and capped with 100 mm of geopolymer concrete, on top of which will be placed an additional 600 mm of top soil. The entire perimeter of the vault will be surrounded with peripheral surface water ditches, resulting in a waste management unit which contains a waste of minimal reactivity and which is isolated from interaction Topaail Low pennwbfllty llnr ~~ Figure 6: Cross-section of Waste ManagementUnitforTreatment of Smelter Yard Waste.
  • 5. with ground and surface water (Figure 6). The unique properties of geopolymer and inorganic binders, including rapid achievement of high strengths and the ability to immobilize chemical toxins even under conditions of acidic leaching, should result in some interesting future applications. REFERENCES COMRIE, D.C. (1988): New Hope for Toxic Waste, IN: The World & I, August, 1988,Publ. Washington Times, pp.171-177. COMRIE, D.C. and DAVIDOVITS, J.(1988): Waste Containment Technology for Management of Uranium Mill Tailings. Presented at the 117th Annual Meeting of the AIMEISME, January, 1988, Phoenix, Arizona. REFERENCES (continued) DAVIDOVITS, J. and COMRIE, D.C.(1988): Archaeological Long-Term Durability: of Hazardous Waste Disposal - Preliminary Results with Geopolymer Technologies. Div. Env. Chemistry, American Chemical Society,Toronto, June, 1988. Preprint. DAVIDOVITS, J. and COMRIE, D.C. (1989): Applications of Geopolymeric Grouts in the Prevention of Environmental Contamination. American Chemical Institute National Convention, Atlanta, February, 1989. Preprint. DAVIDOVITS, J. and DAVIDOVITS, M.(1987): Geopolymer Poly(sialate)/Poly(sialate-siloxo) Mineral Matrices for Composite Materials. Proc. VIth International Conference on Composite Materials, Imperial College, London, UK, July 20-24, 1987. Preprint. Synthesis of new high-temperature Geopolymers for reinforced plastics and composites, SPE PACTEC '79, Costa Mesa, California, Society of Plastics Engineers, USA, 1979, pp. 151-154. Disclaimer The work described in this paper w a s not funded by the U.S. Environmental Protection Agency. The contents do not necessarily reflect the views of the Agency and no official endorse- ment should be inferred.
  • 6. Cement casting and sintering are two treatment techniques for hazar g toxic metals. Research in the wastes. Treatability arsenic-bearing soils nt at the Whitmoyer Laboratories Superfund Site. Treatability study Cement casting was waste combination pri effective in promoting waste stabilization. successful in stabilizing the calcium-arsenic ot effective on the iron- quantities of arsenic aINTRODUCTION The Whitdyer Laborat ries s located in Ja kson Veterihary C o u b t y , arsenic! precipitation in an unhined lagoon. When environmeptal conseqdences from this practice were noted: the sludge was excavated and The site operator condbcted a groundwater pump-and-treat program at 166