Refractories and Industrial Ceramics Vol. 47, No.

5, 2006

REFRACTORIES ABROAD
A STUDY OF THE APPLICABILITY OF WASTE CATALYST
IN HEAT-RESISTANT CONCRETE

I. Pundene,1 S. Goberis,1 V. Antonovich,1 and R. Stonis1

Translated from Novye Ogneupory, No. 8, pp. 58 – 62, August, 2006.

Original article submitted April 19, 2006.

The authors describe the results of studying medium-cement heat-resistant concrete with an additive of waste
catalyst (WC) that is generated at oil-processing plants and compare them with traditional microsilica and
reactive alumina additives. Certain specifics of reactions between aluminate cement Gorkal-40 and the WC
are identified, which accelerate the setting and hardening of concrete. The WC additive facilitates the forma-
tion of anorthite in the concrete matrix, which has a positive effect on the thermal resistance of heat-resistant
concrete.

The petrochemical sector annually generates hundreds of
thousands of tons of waste catalyst (WC). The Mazeikiai Oil
Refinery in Lithuania generates about 200 tons of such waste
every year. Its recycling is very urgent, both in the environ-
mental and economical context. Some countries, for in-
stance, Germany and Holland, use about 5% WC in asphalt
production; about 6% WC is used in cement clinker produc-
tion in France [1]. The recent trend in recycling is using the
WC as a disperse additive to mortar, concrete, and various
portland cement mixtures.
Numerous foreign researchers [2 – 4] have described
their results in studying the interaction between the WC and
portland cement, which identified the pozzolanic effect of
the additive. The purpose of the present study is to investi-
gate certain aspects of the interaction of the WC with
aluminate cement, in order to determine the applicability of a
WC additive in the composition of heat-resistant concrete.
The production cost of heat-resistant concrete could be low-
ered significantly due to the replacement of expensive reac-
tive alumina by a WC additive.
EXPERIMENTS
The following materials were used in the present study:
— Gorkal-40 cement (G-40) produced by the Gorkal
company (Poland) with Al2O3 content not less than 40%.
1 which is a polycarboxylate ester produced by Degussa (Ger-
Thermal Insulation Institute of the Gediminas Vilnius Technical
University, Lithuania.
Its main mineralogical phases are: CA, ferrite, C12A7,
and C2AS; refractoriness at least 1280°C, bulk density
1160 kg/m3;
— reactive alumina (RA) STS-20 produced by Almatis
(Germany), specific surface area 2 m2/g, bulk density
1200 kg/m3;
— microsilica (MS) produced by Elkem (Norway). The
chemical composition of MS (wt.%): Si2O 98.6, Al2O3 0.28,
Fe2O3 0.02, Na2O 0.06, CaO 0.17, MgO 0.09, K2O 0.06, SO3
0.08, Cl 0.01, and P2O5 0.03; bulk density 430 kg/m3, spe-
cific surface area 15 m2/kg, calcination losses at 750°C
£2%;
— spent catalyst waste (WC), which is a mixture of
microspheres of different sizes (20 – 100 ìm). The chemical
composition (wt.%): SiO2 55.2, Al2O3 40.9, Fe2O 0.9, TiO2
1.4, Na2O 0.2, Ni, V, CaO, and MgO — traces; bulk density
830 kg/m3, residue on a 45-ìm sieve 70%. In our study, we
used milled WC; its distribution of particles by sizes (Fig. 1)
was determined using a Fritsch 22 laser analyzer. The bulk
density of the milled WC is 630 kg/m3; calcination loss at
1200°C is 5.9%;
— chamotte components from firebrick of grade ShA,
density 1920 kg/m3, prepared by crushing and milling in a
ball mill; we used milled chamotte and filler of the fraction
<10 mm;
— Castament FS20 deflocculating agent (FS-20),
many).

330
1083-4877/06/4705-0330 © 2006 Springer Science+Business Media, Inc.
A Study of the Applicability of Waste Catalyst in Heat-Resistant Concrete 331

16 B3
43
B4 B6
Content, vol.%

12 39

Temperature, °C
B1
35 B2
8
31
4 27
23 B5
0
0 1 5 10 50 100
19
Particle size, ìm 0 4 8 12 16 20 24 28 32 36 40
Fig. 1. Size distribution of particles of milled waste catalyst. Time, h
Fig. 2. Kinetics of the exothermic effect in concrete depending on
introduced additive.
The main physicomechanical characteristics (apparent
density, compressive strength, shrinkage after heat treatment)
of cubic samples (7-cm edge) of medium-cement, heat-resis- tures B2 and B6 with MS and RA additive, the maximum is
tant concrete after treatment at different temperatures were registered in 14 – 16 h. The most accelerated hydration is ob-
determined according to GOST 20910 and LST EN1402. served in G-40 aluminate cement, caused by the WC (7 – 8 h
Drying and firing of samples were performed according to after mixing with water). This shows that the WC has the
instruction SN 156–79. The velocity of an ultrasonic pulse highest chemical activity among the considered additives.
(USP) in samples was measured with a UK-14P instrument
according to GOST 17624. The exothermic effect in concrete
was measured according to a method developed by Alcoa. THE EFFECT OF HEAT TREATMENT
X-ray phase analysis was performed with a DRON-2 x-ray ON THE PHYSICOMECHANICAL
diffractometer (anticathode — copper, filter — nickel, anode PARAMETERS OF CONCRETE
voltage 30 kV, anode current 8 mA). The phase composition
was identified based on reference data from the ASTM data- For further studies we selected concretes B2, B4, B5, and
base. B6. Their physicomechanical properties were measured after
In order to establish the possibility of using WC addi- 3 days of curing and heat treatment at 110, 800, 1000, 1200,
tives in medium-cement, heat-resistant concrete, we prepared and 1250°C. The measurements of apparent density and
6 concrete compositions (B1 – B6). Three compositions in- shrinkage of the concretes are listed in Table 2. It is estab-
cluded 5% WC additives; namely, mixture B3 had only a lished that a RA additive (B5 and B6) slightly increases the
WC additive, whereas B4 and B5 contained WC combined apparent density of concrete in the whole temperature inter-
with microsilica and reactive alumina additives. For refer- val. We can also note a certain positive effect of this additive
ence purposes, we tested compositions without WC additives on the shrinkage of concrete after heat treatment. At the same
(B2 and B6) that had the same quantities of MS and RA. time, no particular effect of the WC on the apparent density
Table 1 also includes composition B1 without any additives. and shrinkage after heat treatment has been registered
All compositions were prepared with the same content of (B4, B5).
aluminate cement G-40 (12%), milled chamotte (15%), wa- However, a noticeable positive effect of the WC additive
ter (10.5%), and deflocculant FS-20 (0.15%). Water and on the compressive strength of concrete has been established
deffloculant were introduced above 100% dry components. (Fig. 3). The functional dependence of strength on heat-treat-
ment temperature is virtually identical in all concretes: a
Important information was obtained studying the kinetics
of heat emission from hardening concrete (Fig. 2). The con-
cretes with the WC additive (B3, B4, and B5) have a typical
TABLE 1. Compositions of Medium-Cement Concretes with Vari-
initial exothermic effect, which starts in the interval of
ous Additives
45 – 50 min and ends 20 – 30 min later, virtually regardless
of the other additives (MS, RA, or combined MS + RA). In Content of the component, %
Concrete
this case, the temperature grows by 2 – 3°C and then remains composition Chamotte of fraction
WC MS RA
virtually constant for 6 – 6.5 h until the beginning of the £10 mm
main exothermic effect. This initial exothermic effect is per- B1 — — — 73
ceptibly weaker in compositions B2 and B6 containing MS B2 — 5 — 68
and RA additives and does not exist in B1. The reasons for B3 5 — — 68
this initial exothermic effect require additional investigation. B4 5 5 — 63
The time of emergence of the main temperature peaks on B5 5 5 5 58
the curves also depends on the type of additives in the con- B6 — 5 5 63
crete. The main exothermic maximum in mixture B1, which All mixtures contain 12% G-40, 15% milled chamotte, and also
has no additives, is observed only after 22 – 24 h; in mix- 0.15% FS-20 and 10.5% water above 100%.
332 I. Pundene et al.

50 strength parameters are registered when using a combination

B2 B4
45 B5 B6 of three additives (MS + RA + WC).
40
The ultrasonic study of the same concretes yielded a sim-
ócompr, MPa

ilar dependence of the USP on the firing temperature of sam-

35 ples (Fig. 4). After the removal of free moisture (20 – 110°C)
30 and decomposition of crystal hydrates (110 – 800°C), the
value of the USP sharply decreases and then increases at a
25
higher temperature, as a consequence of the transformation
20 of the concrete structure and the formation of new minerals
20 110 800 1000 1200 1250
t, °C (the interval of 800 – 1250°C).
Fig. 3. Compressive strength ócompr of concrete depending on their
treatment temperature t.
THE EFFECT OF WC ON THE MINERAL
COMPOSITION OF HIGH-TEMPERATURE
COMPOSITES WITH GORKAL-40 CEMENT
4000 B2 B4
B5 B6 To clarify the specifics of new formations in the matrices
of the considered concretes after heat treatment (800 –
USP, m/sec

3500
3000
2500
2000
20 110 800 1000 1200
t, °C
Fig. 4. Variation of USP velocity in concrete samples depending on
their treatment temperature t.
compressive-strength minimum exists within the range of
800 – 1000°C and a perceptible increase is registered after
firing at a higher temperature, which is caused by the forma-
tion of new minerals and sintering of the structure. Yet the
curve of B2 without WC and having only an MS additive is
significantly lower than the curves of B4 and B5. This means
that the WC additive combined with MS and RA perceptibly
increases the strength of the concrete. Comparing curves B4
and B6, it can be concluded that the combination of two ad-
ditives (WC + MS or RA + MS) has a virtually equal effect
on the strength of concrete in the entire temperature interval
from the curing of concrete up to 1250°C. This conclusion
appears important, since replacing very expensive reactive
alumina by an equal quantity of WC in a heat-resistant con-
crete can achieve similar strength characteristics. The highest
1250°C), samples of high-temperature mixtures without cha-
motte and deflocculant were prepared. All mixtures (2 – 6)
included 100 g of G-40 cement, 100 g of water, and 30 g of
each additive (WC, MS, and RA). The additives used are in-
dicated below:
1250
Mixture 2 4 5 6
Additive MS WC + MS WC + MS + RA MS + RA
The diffraction patterns of each mixture indicate quanti-
tative variations in the content of minerals in the samples,
which is reflected in the intensity of the main diffraction
maxima of the considered minerals. The peak intensities of
the following minerals have been measured: helenite C2AS,
cristobalite, anorthite CAS2, calcium aluminate CA, and the
ferrite phase.
The differences between these compositions fired at
800°C are minimal; the diffraction patterns of all mixtures
show the prevailing helenite and ferrite phases; a certain
quantity of CA is observed as well. It is known [5,
pp. 376 – 395] that helenite virtually does not react with wa-
ter; therefore, the height of the helenite peak in all mixtures
varies insignificantly under heating to 800°C. The main dif-
ferences between the compositions are manifested after fir-
ing at 900°C.
The mixtures with WC (4 and 5) exhibit additional crys-
tallization of helenite (Fig. 5a) earlier by 100°C than the
mixtures without WC (2 and 6); moreover, the content of

TABLE 2. Apparent Density and Shrinkage of Concrete Treated at Different Temperatures

Apparent density, kg/m3 Shrinkage, %
Concrete
after heat treatment at temperature, °C
composition
20 110 800 1000 1200 1250 800 1000 1200 1250
B2 2110 2030 1960 1960 1960 1960 –0.14 –0.14 –0.14 –0.28
B4 2130 2040 2040 1970 1970 1970 –0.14 –0.14 –0.14 –0.14
B5 2180 2100 2050 2020 2020 2020 –0.14 –0.14 –0.14 –0.14
B6 2160 2080 2020 2010 2010 2010 0 0 –0.14 –0.14
A Study of the Applicability of Waste Catalyst in Heat-Resistant Concrete 333

350
a b
2
300
6
Peak height, mm 250 4
200 5

150

100

50

0
800 900 1000 1200 1250 900 1000 1200 1250
Fig. 5. Crystallization of helenite (a) and anorthite (b) in mixtures after firing at different temperatures.

helenite in mixtures 4 and 5 after firing at 1250°C decreases. 120

a b
2
Apparently, the presence of the WC in mixtures facilitates an 100
6
earlier and more intense crystallization of helenite.

The formation of anorthite in compositions 4 and 5
(Fig. 5b) is registered at a temperature 100°C lower than in
the rest of the mixtures; a significant increase in the amount
of anorthite is observed in compositions 4 and 5 after firing
at 1200 – 1250°C. It is essential that anorthite be the predom-
inant mineral in mixtures 4 and 5 after firing within the range
of 1200 – 1250°C, whereas in mixtures 2 and 6 the crystalli-
zation of anorthite is much less perceptible than that of
helenite. Analysis of diffraction patterns suggests that MS
without a WC additive facilitates the formation of helenite as
the main mineral, whereas anorthite becomes the main min-
eral in mixtures with WC.
After firing of 900°C, all mixtures exhibit the formation
of a small quantity of cristobalite (Fig. 6a), since all mixtures
contain an MS additive. Our previous studies [6] established
that intense crystallization of cristobalite starts at 1100°C.
Cristobalite can be formed at a lower temperature if calcium
and sodium ions diffuse into its structure. It is known [7] that
hydration of CA leads to the formation of Ca(OH)2 together
with calcium hydroaluminates, and the former reacts with
microsilica while hydration is still in progress. The diffusion
of calcium and aluminum ions into microsilica is intensified
due to the effect of high temperature; consequently, calcium
aluminosilicates are formed and microsilica that has not par-
ticipated in the reaction is crystallized in the form of
cristobalite [8]. An intense growth of cristobalite content in
mixtures 2 and 6 is observed up to 1200°C; its formation de-
creases perceptibly after firing at 1250°C. The mixtures con-
taining WC do not exhibit cristobalite after firing at 1200°C,
presumably due to the more intense crystallization of anor-
thite.
The crystallization of mineral CA (Fig. 6b) prevails in
the mixtures with intense crystallization of helenite (compo-
sitions 2 and 6) up to 1000°C. However, after firing at
1200°C mineral CA starts crystallizing in mixtures with in-
tense crystallization of anorthite. After firing at 1250°C, CA
has not been identified in any mixture.
Peak height, mm
80 4
5
60
40
20
0
900 1000 1200 1250 800 900 1000 1200
Fig. 6. Crystallization of cristobalite (a) and mineral CA (b) in mix-
tures after firing at different temperatures.
The quantity of the ferrite phase in all mixtures decreases
with increasing temperature, and after firing at 1250°C this
phase is absent.
The described x-ray phase analysis offer comments on
the strength parameters of the considered concretes. After
firing at 1000°C, the highest strength is observed in concrete
B5, whose matrix exhibits a perceptible growth of anorthite.
The lowest strength is registered in the concrete with the
microsilica additive, since helenite prevails in its matrix and
cristobalite is observed as well, which is undesirable in view
of the volumetric modifications occurring in the transforma-
tion of â-cristobalite into the á-phase [9]. The more intense
the crystallization of anorthite (concretes containing WC),
the higher their strength after firing at 1200°C. Further firing
of concrete B5 at 1250°C corroborates the tendency toward
increasing strength in the case of additional crystallization of
anorthite.
DESTRUCTION OF CONCRETES
UNDER CYCLIC TEMPERATURE IMPACT
In our study, an attempt was made to correlate variations
in the mineral composition of mixtures with variations of the
USP in concrete under a cyclic temperature impact. For this
purpose, we have used the method of slow heating and cool-
ing cycles of concretes and composites in a furnace after
which the USP in the concrete sample was measured. This
334
120 a
and cristobalite peaks, mm
80
Height of anorthite
40
0 75
300
b
200
100
0 92
B2 B6 B4
Concrete composition
Fig. 7. Relative USP in concretes after 5 thermal cycles at 1000 (a)
and 1200°C (b) correlated with the content of anorthite and
cristobalite in the matrix: ¢, USP; ˜, anorthite; ™, cristobalite.
value of the USP in concrete after a first firing is taken as
100%; the USP after 5 firing cycles is estimated as a percent-
age of the USP measured after the first firing.
The relative USP values in concrete samples after 5 ther-
mal cycles at 1000 and 1200°C are compared with the anor-
thite and cristobalite peaks in the mixtures, also after 5 ther-
mal cycles (Fig. 7).
It is found that concrete B2 is the most prone to destruc-
tion after 5 thermal cycles at 1000°C. The relative USP in
this concrete decreases to 84%; the cristobalite peaks in its
matrix have the maximal values and the anorthite peaks have
the minimal values. After 5 cycles at 1200°C, the relative de-
crease in the USP of this concrete is lower and the values of
newly formed peaks are significantly higher. The concrete
B5 containing all considered additives is not at all prone to
destruction (99% USP). These differences between the con-
cretes and their matrices are probably caused by the fact
that at 1000°C the formation of anorthite and cristobalite is
not completed, whereas at 1200°C the crystallization pro-
cesses approach their completion. Its is also known that anor-
thite has a low coefficient of linear temperature expansion
(4.82 ´ 10–6 K–1), which facilitates an increased heat resis-
tance of concretes.
I. Pundene et al.
100 CONCLUSIONS
95
90
Relative USP value, %
As a consequence of the studies performed, the possibil-
85
ity and advisability of adding spent catalyst waste to medi-
80
um-cement, heat-resistant concrete based on Gorkal-40 alu-
100 minate cement has been established. It is found that hydra-
98 tion of cement with a waste-catalyst additive is significantly
96 faster than that of concrete without this additive. A 5% WC
94
additive perceptibly improves the strength parameters of
concrete, especially combined with microsilica and reactive
B5 alumina additives.
X-ray diffraction analysis of concrete matrices with a
WC additive after high-temperature firing identified an in-
creased content of anorthite in the matrix structure.
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