THEODOR STANK, LENKA SCHWARZEROV*

UTILIZATION OF NATURAL WASTE POZZOLANA

UTYLIZACJA ODPADW NATURALNEJ PUCOLANY
Abstract
The goal of this paper is to show new possibilities of the natural waste pozzolana utilization.
First, waste diatomaceous earth containing higher portion of clay minerals - which is not suitable for
filter use in food industry - was chosen for our experimental work. Our tests were focused on the study
of preparation of cementitious binders containing waste diatomaceous earth. Standard cement pastes with
10%, 15%, 20% and 30% replacement of cement with calcined waste diatomite were examined, calcination
temperature was 650C. Simultaneously technological properties of prepared binders were tested and results
were compared with the standard for Portland cement. Our binders with diatomaceous earth showed slightly
lower early strengths but favourable higher long-term compressive strength and lower heat of hydration.
Next our attention was given to another waste pozzolana, waste kieselguhr sludge generating during
deep bed filtration of beverages (wine, beer, juice). The kieselguhr is prepared from diatomaceous earth
by crushing, drying and calcining at temperature 8001200C successively. Currently, the most frequent
disposal method is to spread the used kieselguhr over agricultural land. Presently basic chemical, physical
and technological tests of a sample of kieselguhr waste coming from Czech brewery are taking place.
Keywords: diatomaceous earth, kieselguhr, cement binder, calcination, technological properties
Streszczenie
Celem niniejszej pracy jest pokazanie nowych moliwoci utylizacji odpadw naturalnej pucolany. Do
pracy wybrano diatomit zawierajcy nadmiern ilo mineraw ilastych, ktra nie moe by wykorzystana
do filtracji w przemyle spoywczym. Przeprowadzono prby otrzymywania cementowych materiaw
wicych zawierajcych odpadowy diatomit. W badaniach cement zastpowano dodatkiem diatomitu,
kalcynowanego w temperaturze 650C. W otrzymanych materiaach badano podstawowe parametry
uytkowe, ktre odnoszono do materiaw zawierajcych cement portlandzki. Prbki zawierajce diatomit
pocztkowo wykazyway nisz wytrzymao na ciskanie oraz wysz wytrzymao dugoterminow.
Wykazyway ponadto nisze ciepo hydratacji. Dalsze badania prowadzono z innymi odpadami pucolany,
szlamami ziemi okrzemkowej, powstajcymi w procesie filtracji napojw (wina, piwa, sokw). Ziemia
okrzemkowa jest otrzymywana z ziemi diatomitowej w wyniku mielenia, suszenia i kalcynacji w temp.
8001200C. Obecnie, odpadow ziemi okrzemkow wykorzystuje si w rolnictwie. Prowadzone s
podstawowe badania waciwoci fizycznych i chemicznych oraz testy technologiczne nad wykorzystaniem
odpadowej ziemi okrzemkowej z czeskiego przemysu browarniczego.
Sowa kluczowe: diatomit, ziemia okrzemkowa, spoiwo cementowe, kalynacja, waciwoci technologiczne
*

PhD. Eng. Theodor Stank, Eng. Lenka Schwarzerov, Research Institute of Building, JSC., Brno,
Czech Republic.

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1. Introduction
Rapidly developing building industry demands new improved cement-based building
materials. Therefore the area of cementitious binders develops extensively, there are new
ways of cement preparation with non-traditional materials and endeavour to extend blended
cement categories [1, 2]. However, the preparation of new cements is strongly limited, if
not excluded by standard EN 197-1. Implementing of non-traditional materials into cement
binders demands attentive research into newly-formed materials properties.
The work was divided into two parts.
First we fixated cement mixtures with a content of thermally modified diatomaceous
earth (H4). Experiments proceeded in several steps. Primarily the influence of various main
raw material additions on properties of the resulting cement mixture was monitored. Raw
material was calcined in a further step. The influence of FGD-gypsum (setting controller)
replacement by anhydrite II which was made from FGD-gypsum in mixture with calcined
raw material was monitored in the last step. A cement prepared in laboratory from clinker and
FGD-gypsum was used as the reference standard (M0), the same cement was used for cement
mixtures with diatomaceous earth (excluding the last step with anhydrite II). Compressive
strength development, hydration heat evolution and process of setting of prepared cement
mixtures were monitored. Evolution of microstructure and products of hydration was
examined on selected samples as well.
The second part of the work attends to a possible reuse of a waste kieselguhr sludge in
building industry, namely as an addition to concrete composites or as a raw material for
geopolymer preparation. Kieselguhr is made from treated diatomaceous earth by calcining at
temperatures of 800 1200C and it possesses pozzolana properties. At present, approximately
1.8 million tons of diatomaceous earth for kieselguhr production are mined every year [3].
Two-third of the manufactured kieselguhr is used as a filter medium in beverage industry (beer,
wine, fruit juice and liquors) [4]. Usually kieselguhr sludge coming from deep bed filtration
process is disposed of after filtration and it can be used for the recultivation of landscape
or be taken to a waste dump. Presently basic chemical, physical and technological tests of
two samples of waste kieselguhr sludge coming from two Czech breweries are taking place.
2. Experimental
2.1. Experimental with waste diatomaceous earth
The cement M0 was replaced by 10, 15, 20 and 30 wt.% of diatomaceous earth in the first
step. The M0 cement was prepared from industry clinker and FGD-gypsum. Replacement
levels of 20 and 30% were used in the second step, mixtures were prepared from cement
M0 and ground diatomaceous earth calcined at 650C. The replacement level of cement
with diatomaceous earth was the same in the third step, cement was prepared from industry
clinker and anhydrite II which was prepared by thermal treatment of FGD-gypsum. Specific
surface of anhydrite II was the same as for standard M0 (around 340m2/kg). Cement mixtures
description and their composition is listed in Tab. 1.

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Ta b l e 1

Description

Clinker

FGD-gypsum

Anhydrite II

Cement M0

Cement M0A2

Diatomaceous earth H4

Calcined diatomaceous
earth H4K-650

Cement mixture description and their compositions in wt.%

M0

95

M0A2

96

M10H4

90

10

M15H4

85

15

M20H4

80

20

M30H4

70

30

M10H4K-650S

90

10

M20H4K-650S

80

20

M10H4K-650A2

90

10

M20H4K-650A2

80

20

2.1.1. Compressive strength

Compressive strength tests according to standard EN 196-1 were measured on standard
bars after 2, 7, 28, 56 and 90 days of hydration. Results of all three steps are given in Table 2.
2.1.2. Normal consistency, start and period of setting
Measurements followed standard EN 196-3. Results are given in Table 3.
2.1.3. Heat of hydration
Semi-adiabatic calorimetry allowed us to study thermal changes due to chemical reactions
of cement suspensions and other mortars in time dependence [5]. During the measurement
there is a reaction pot which is isolated with steam-proof lid placed in metal mantle with
heat-transfer winding. One thermal sensor is placed in the reaction pot and the second one is
placed externally on insulating mantle. The measurement proceeded in isoperibolic mode at a
constant mantle temperature of 35C for 24 hours, water to cement ratio was 0.35. The results
of the measurement are shown in Figures 1 and 2.

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Ta b l e 2
Compressive strength development of cement mixtures in MPa
Sample

2 days

7 days

28 days

56 days

90 days

M0

24.2

48.5

62.5

66.6

68.8

M10H4

17.1

36.2

54.7

56.7

60.0

M15H4

13.3

32.0

49.5

55.6

57.4

M20H4

9.3

26.3

44.9

49.8

51.8

M30H4

6.1

10.7

18.2

18.5

24.6

M10H4K-650S

20.8

47.8

68.6

75.5

76.4

M20H4K-650S

17.0

41.3

62.5

74.2

76.1

M10H4K-650A2

21.9

49.9

71.4

74.9

77.9

M20H4K-650A2

17.3

45.5

69.9

76.3

77.9

Ta b l e 3
Normal consistency and setting of fresh cement mixture
Normal consistency
w/c [%]

Start of setting
[hours:min]

Period of setting
[hours:min]

M0

27.7

4:50

5:50

M10H4

33.3

4:30

6:10

M15H4

37.0

4:30

7:20

M20H4

41.0

4:30

7:00

M30H4

48.0

3:50

6:10

M10H4K-650S

31.7

4:00

4:50

M20H4K-650S

33.3

3:50

4:50

M10H4K-650A2

32.7

3:50

4:40

M20H4K-650A2

35.0

3:20

4:20

Sample

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Fig. 1. Hydration heat evolution with different levels of diatomaceous earth

Rys. 1. Zmiany ciepa hydratacji w zalenoci od zawartoci diatomitu

Fig. 2. Hydration heat evolution with diatomaceous earth and different setting controllers
Rys. 2. Zmiany ciepa hydratacji materiaw z dodatkiem diatomitu oraz rnymi regulatorami
prdkoci wizania

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2.1.4. Differential thermal analysis (DTA) of cement stone
The same samples as those for hydration heat evolution were used for DTA. Samples
were stored in water bath for 28days and then the hydration was stopped by multiple washing
of crushed material with ethyl alcohol and acetone. Thermographs of samples were made by
Netzsch STA 429 apparatus in a temperature range of 301050C.
Individual processes that were monitored in the samples can be summarized as follows:
Distinct endotherm with minimum at 150180C belongs to loss of water bound in C-S-H
products. The endotherm with minimum at 195210C belongs to dehydration of ettringite.
The endotherm with minimum at 420460C refers to dehydration of C-A-H. Another
endotherm with minimum at 510540C is related to dehydrogenation of portlandite. The
following double endotherm is related to decarbonation of calcite (CaCO3) with minimum
at 680800C and 770840C. Quantitative evaluation using ScopeWin software is shown
in Table 4.
Ta b l e 4
Quantitative evaluation of thermographs in wt. %
Sample

H2O bound in C-S-H

and ettringite

H2O bound in
C-A-H

Ca(OH)2

CaCO3

LOI

M0

11.3

1.0

13.1

9.5

19.6

M10H4

11.6

1.5

12.8

5.8

19.4

M20H4

11.9

1.1

10.8

7.3

19.6

M10H4K-650S

13.0

0.8

9.6

10.1

20.6

M20H4K-650S

13.6

1.2

5.3

9.1

21.0

M10H4K-650A2

12.8

0.8

9.0

7.3

20.0

M20H4K-650A2

15.4

1.0

5.7

7.2

21.5

2.1.5. Porosity of cement stone

Samples for porosity measurement and DTA were cured under the same conditions.
Mercury pressure porosimeter Carlo Erba 200 was used for porosity measurement. Results
of bulk porosity are given in Table 5.
Ta b l e 5
Bulk porosity of cement stone
Sample

M0

M10H4

M20H4

M10H4K650A2

M20H4K650A2

Bulk porosity
[cm3/g]

0.1246

0.1279

0.1313

0.0974

0.1107

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2.2. Experimental with kieselguhr sludge
Two samples of waste kieselguhr sludges used for the experimental work originated from
two Czech breweries. Both samples were dried at a temperature of 50C. The drying process
was accompanied by the evolution of strong odour coming from a decomposition of the
organic components (raw protein, nitrogen, glucose) in kieselguhr sludges. The samples were
marked as kieselguhr 1 and kieselguhr 2.
At first the particle size distribution of the two samples was determined by means of
alaser diffraction method and it is displayed in Fig. 3.

Fig. 3. Particle size distribution of kieselguhr 1 and kieselguhr 2 using laser granulometer CILAS,
dispersing medium isopropanol
Rys. 3. Rozkad ziarnowy ziemi okrzemkowej 1 i 2

Next, differential thermal analyses and X-ray diffraction analyses of kieselguhr sludges
were carried out, presently the results are being processed.
Two cement mixtures were prepared for the determination of normal consistency
according to EN 196-3. In these cement mixtures (mixture 1 and mixture 2) a cement CEM
I 52.5 N was replaced by 10wt. % of kieselguhr 1 and kieselguhr 2, respectively. The results
are summarized in Table 6.
The determination of the start and the end of setting was carried out according to EN 1963 using the automatic Vicat apparatus. The same cement mixtures as for normal consistency
determination were used (see above). The results are shown in Table 6.
The same tests were done also with mixture 0 with cement CEM I 52,5 N without any
addition of kieselguhr sludges.

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Ta b l e 6
Normal consistency
Sample

Normal consistency
w/c [%]

Start of setting
[hours:min]

Period of setting
[hours:min]

Mixture 0

30.7

3:50

5:00

41.0

5:10

6:50

44.3

4:30

6:50

Mixture 1
(10 wt.% of kieselguhr 1)
Mixture 2
(10 wt.% of kieselguhr 2)

3. Conclusions
With respect to strength results, the calcined diatomaceous earth as compared to the
untreated diatomaceous earth improves the compressive strength of prepared mixtures.
Mixtures with anhydrite II as the setting controller showed good early strengths during early
stages of hydration in comparison to mixtures with FGD-gypsum.
Calcined diatomaceous earth mixtures showed better properties with lower water
consumption than those with untreated diatomaceous earth. The time of the start of the setting
is shorter for both calcined and untreated diatomaceous earth compared with the reference
sample. The start of the setting came earlier when calcined diatomaceous earth mixtures were
used and even quicker when anhydrite II was used.
Hydration heat evolution graphs revealed that mixtures with untreated diatomaceous earth
produce lower hydration heat compared with the reference sample. Calcined diatomaceous
earth gave both lower heat of hydration and better long-term strengths compared with the
reference sample.
DTA analyses showed an increase of hydration product content in cement stone and
therefore proved a positive role of diatomaceous earth addition.
Cement stone prepared from mixtures with untreated diatomaceous earth showed higher
porosity whereas calcined diatomaceous earth mixtures showed lower porosity as compared
to the reference sample.
Laboratory results show that cement binder of very good technological properties can be
prepared from Portland cement clinker, ground calcined waste diatomaceous earth and proper
setting controller. Replacement of Portland cement and anhydrite II mixture by 1020% of
ground calcined diatomaceous earth brought 10% lower 2d strength, equal 7d strength and
even 15% higher 28d, 56d and 90d strengths. Mixtures with diatomaceous earth showed
lower heat of hydration and the process of setting wasnt affected distinctively. This new less
energy consuming binder with 20% replacement level has, except for 2d strengths, equal or
better properties than Portland cement CEM I. This binder seems to be applicable for the
preparation of cement composites.
Kieselguhr sludges coming from beer deep bed filtration were tested in order to check
their future possible utilization in building industry. Both kieselguhrs 1 and 2 show higher

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water consumption due to a large specific surface of kieselguhrs. Also the start and the end
of setting with 10wt.% of kieselguhr in cement mixtures are delayed in comparision with the
sample without a kieselguhr addition. Presently further laboratory tests of two samples of
kieselguhr sludges are proceeding.
This paper was elaborated due to the project Ministry of Education, Youth and Sports of the Czech
Republic n. MSM 2623251101 Research of ecological processing of industrial waste materials.

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