.

, 2008

2003
2008
() .
,
, . ,

.

.
.
.

,

.
.
.
..


.
. .

,
.


, . , .
. . .

.
,

,


.

, ,

.


, ,
.
.
,
, , , ,
.. ,
.... , ,
.

.
, ,
,

. ...
6


..................................................................................... 9
SUMMARY .................................................................................... 13
1. ............................................................................ 17
1.1 ...................................................................................................................................17
1.2 ............................................................................19
1.2.1 ...........................................................................................................19
1.2.2 ..........................................................................................................................21
1.2.3 ..................................................................................................................22
1.2.4 .......................................................................................................................22
1.3 ............................................................................................23
1.4 ........................................................................................................23
1.5 ...................................................................................................25
1.5.1 ...............................................................................................26
1.5.2 .........................................................................................26
1.5.3 ..............................................................................................26
1.5.4 .......................................................27
1.5.5 .....................................................................................................27
1.5.6 ..................................................................................................................27
1.6 ............................................................................................................................29

2. ...................................................................... 37
2.1 ....................................................................................................38
2.1.1 ..........................................................................................................................38
2.1.2
......................................................................................................................................................41
2.1.3 .............................................42
2.1.4 .................................45
2.2 ............................................................49
2.2.1 ..........................................................................................................................49
2.2.2 ..............................................................................49
2.2.3 ..................................................................51
2.2.4 ..................................................................52
2.2.5 ................................................53
2.2.6 .....................................................................55
2.2.7 ...........................................................57
2.3 ........................................................................................................................58
2.4 ............................................................................................................................59

3. ...... 61
3.1 ........................................................................................................62
3.1.1 ..........................................................................................................................62
3.1.2 .....................................................................................................................68
3.1.3 ....................................................................................................70
3.1.4 .............................................................................................72
3.1.5 ........................................................................................................75
3.1.6 .....................................................................................................83
3.1.7
.........................................................................................................................................86
3.2 .........................................................................................................89
3.2.1 ..........................................................................................................................89
3.2.2 .....................................................................................................................89
3.2.3 () ..................................................................................90
3.2.4 ...............................................................................................91

3.2.5 ....................................................................91
3.2.6 .....................................................................................................92
3.3 ........................................................................................................................94
.3...............................................................................................................................97
3.4 ............................................................................................................................99

4.
.............................................. 105
4.1 .................................................................................................................................106
4.2
...............................................................................................................................111
4.3 ..................................................114
4.3.1 ........................................................................................................................114
4.3.2
.....................................................................................................115
4.3.3 .......120
4.4 ......................................................................................................................124
.4.............................................................................................................................126
.4 ............................................................................................................................131
4.5 ..........................................................................................................................132

5.
......................................... 135
5.1 .................................................................................................................................135
5.2 ..........................................................................................................................139
5.2.1 ................................................139
5.3 .........................................................................................................142
5.4 ................................................................................................................144
5.5 ............................................................................................................145
5.6 ......................................................................................................................146
5.7 ......................................................................................................................151
.5.............................................................................................................................153
B.5 ............................................................................................................................156
.5 .............................................................................................................................158
.5 .............................................................................................................................159
5.8 ..........................................................................................................................161

6.
.............................................................. 165
6.1 .................................................................................................................................165
6.2
............................................................................................................................170
6.2.1 ....................171
6.2.2 .............................................173
6.3 .....................174
6.4 .................178
6.5
PORTLAND .....................................................183
6.6 ......................................................................................................................187
6.7 ..........................................................................................................................189

7. .................................................................... 193

,
,
.

Bayer.
,
,

.

, .
,

.
,

()

~35% .
,
.

27% 32%

2g/cm3,

,
2006 .


.

Portland

5%..



.

42.5N.

(52.5N) (2 ).
,

,
.


2.7%.
.

Mn, Pb, Zn Cu
Cr.

27.7MPa 2 51.6MPa
28 .
,
.

,
.
,

()

2%.

.
10

 , NEN 7345-tank test

(service life scenario) prEN 14429-pH dependence test
(second life scenario).
,
Cr, Ni V
.
, Cr
Ni V

. ()


pH.



.
Portland
(C3S)
(~1350C)
.


Portland, .


4CaO.3Al2O3.SO3 .

(Cr(VI))

pH ,
11

 (l:s ratio).


.
10m2 g-1 70m2 g-1
.

0.82mg g-1.
Langmuir pH
5 6.

12

Summary

In the present thesis the potential utilization of ferroalumina, a byproduct that derives from the dewatering of red mud, as a raw
material as well as an additive material in the cement production
route is examined.
Red mud is the main by-product that derives from the digestion of
bauxite ores during Bayer process in order to produce alumina. It
comprises from the ore part that has not reacted, the part that has
reacted and has formed other than the desired compounds, from
supplementary materials that were introduced during the procedure
and from aluminium hydroxides that were not recovered.
The removal of red muds water content leads to the production of
ferroalumina. Although there are many ways of removing the water,
the use of a filter press has many advantages. The laboratory study of
the water removal from red mud by means of a filter press led to the
formation of a cake with ~35%wt of water. Parameters, such as the
filter type and the material that it comprises were examined with the
further use of a pilot scale filter press. The results indicated that the
filter press can produce a cake with constant water amount between
27% and 32%wt and density 2g/cm3. The latter results, led to the
installation of an industrial high pressure filter press, which is in
operation since the beginning of 2006, in the Aluminium Hellas
industry.
Ferroaluminas chemical analysis indicates that it can be used as a
secondary material in the cement industry, mainly as an iron oxide
carrier. The study for its suitability was performed by preparing
Portland cement raw mixtures introducing ferroalumina up to 5%wt
are a raw material. Consequently, the raw mixtures were fired up to
1550oC in order to produce clinker and co-grounded with gypsum in

13

order to produce Portland cement. The results indicate that the

produced

ferroalumina

cements

presents

similar

mineralogical

composition with the cements without ferroalumina whilst their

physical properties such as the water demand and the setting time are
at the same levels. Regarding their mechanical properties, the
obtained compressive strength values are ranking all the cements in
the 42.5N category. Especially the ferroalumina cements are falling
into a higher category and more specifically in the 52.5N category due
to their high early day strengths. Finally, the study indicate that the
ferroalumina cements presents higher amounts of water soluble
chromium than the cement without ferroalumina (reference), most
probably due to their higher initial amount of total chromium.
The industrial trials that were performed by the Greek cement
industries TITAN and AGET Heracles showed that the addition of
ferroalumina up to 2.7%wt improves the burnability of the mixture
due to the silica modulus reduction. The substitution of the raw
material pyrite from the ferroalumina, led to the reduction of Mn, Pb,
Zn and Cu on the raw mixture whilst it increased the Cr percentage.
The results for the produced clinker indicate that the ferroalumina
addition did not affect the formatted mineralogical phases. The
compressive strength values of the obtained cements, was 27.7MPa
after the first 2 days and 51.6MPa after 28 days of curing. The flue
gas emissions were at the same levels during the cement production
indicating that the ferroalumina addition does not affect that part of
production either.
In order to evaluate the environmental behaviour of the ferroalumina
cements, two types of leaching tests, which refer to different field
scenarios, were employed. The NEN 7345-tank test which refers to
monolithic materials (service life scenario) and the prEN 14429-pH
dependence test, which concerns granular materials (second life
scenario). Two different cement samples were used for the above
mentioned tests. The first one was produced without ferroalumina
14

(reference sample) whilst the second one was produced with a 2%wt
ferroalumina addition. The chemical analysis of the cement with
ferroalumina showed that it presents greater content of Cr, Ni and V
than the reference cement. The latter does not affect leaching in the
service life scenario. More specifically in the case of Cr the reference
cement presents the same leaching amount with the ferroalumina
cement whilst in the case of Ni and V no leaching is observed for any
of the two cement samples. During the second life scenario the
leaching is greater in the case of the ferroalumina cement. The latter
is related to the greater initial content of the above mentioned cement
in Cr, Ni and V. The leaching behaviour is for both cements pH
sensitive as higher leaching values for Cr and Ni are observed while
the pH shifts to lower values.
The new trends concerning the sustainable development through
energy conversion and environmental protection have led the current
study in the utilization of ferroalumina in the field of belite cements.
The main difference of the above mentioned cements from the
Portland cements is the low content in calcium silicate (C3S) mainly
due to the lower firing temperature (~1350C). The latter ranks the
above mentioned cements in the environmental friendly cements
category (green cements). The obtained results indicate that the use of
ferroalumina as a raw material for the production of belite cements is
possible as well as that the produced cements have a certain
drawback when compared with the OPC. The lack of C3S leads to low
early

day

strength.

This

drawback

was

confronted

with

the

introduction of gypsum in the raw mixture which led to the formation

of the hydraulic compound 4CaO.3Al2O3.SO3 (Kleins compound)
during the firing procedure.
The last chapter deals with the possibility of utilize ferroalumina as a
substrate for the absorption of hexavalent chromium in order to use it
as an additive material in the last stage of cement production. The
study examined parameters such as the pH of the solution, the
15

contact time and the liquid to solid ratio (l:s ratio). The results
indicate that the ferroalumina is able to absorb chromium and that
this ability increases if a stage of chemical and thermal treatment is
employed before. The treatment enhances ferroaluminas absorption
ability due to an increase of specific surface from 10m2 g-1 to 70m2 g-1.
The absorbance mechanism is described with the Langmuir model
and the best results are obtained for pH 5 and contact time 1h. The
amount of chromium that is absorbed from each grammar of
ferroalumina in the above mentioned conditions is 0.82mg.

16

1.

Bayer. Bayer
,
.
.
,
,
.
,
,
.
,
,
.

1.1
1877 Karl Josef Bayer
,


. ,
(gel) . Bayer

1888,
.
Bayer

. 1
1.9 3.6 ,

17

1.

Bayer.

.
(digestion), (clarification/settling),
(precipitation) (calcination). 1.1.1
Bayer.

1.1.1. Bayer.

.
(NaOH),
(CaO/Ca(OH)2)
.
Bayer
6.8Mt 13% [1.1].

Bayer

18

1.

1.2
1.2.1
,
<150mm
<25mm.
(NaOH)
(CaO). ,
60% <63m.
, -
- 90%
.

.

, ,
.
140-260oC. 240oC 35atm
[1.2]. 1h.

(. ).
-

.
.

Al (OH ) 3( s ) NaOH ( aq ) NaAl (OH ) 4 ( aq )

(1.2.1.1)

19

1.

AlO(OH ) ( s ) NaOH ( aq ) H 2 O NaAl (OH ) 4 ( aq )

(1.2.1.2)

.
.
[1.3]

( Al 2 (OH ) 4 ( Si 2 O5 ) 6OH

H 2 O 2 SiO 2 (OH ) 2

2 Al (OH ) 4

2SiO2 (OH ) 2 2 Al (OH ) 4 2 Na

Na2OAl2O3 2SiO2 (2 k ) H 2O 4OH (2 k ) H 2O

(1.2.1.3)

(1.2.1.4)

k 0-2.
(>140oC), 1.2.1.3
Na+

3( Na2O. Al2O3 .2 SiO2 .2 H 2O ).2 Na2 X

(1.2.1.5)

X 2OH-, CO3-2, SO4-2, 2Cl-,

2AlO2 Na-/Ca-

3( Na2OAl2O3 2 SiO2 )2 Na2CO3 2 H 2O 2Ca (OH ) 2
3( Na2OAl2O3 2 SiO2 )2CaCO3 2 H 2O 4 NaOH

(1.2.1.6)

- ,
.
[1.4].

20

1.

TiO2 Na 2 O Na 2TiO3

(1.2.1.7)

2TiO2 Na 2 O Na 2Ti 2 O5

(1.2.1.8)

TiO2 CaO CaTiO3

(1.2.1.9)

1.2.2
,

.
(),

.
.


. ,

.
, ,

.

.

21

1.

1.2.3

,
.
. ,

.
35h.

.
NaAl (OH ) 4( aq ) Al (OH ) 3( s ) NaOH ( aq )

(1.2.3.1)

.
.



.

1.2.4

.
-
>960oC.
,
22

1.

2 Al (OH ) 3( s ) Al 2 O3( s ) 3H 2 O( g )

(1.2.4.1)

Bayer

0.01% 0.2-0.6%.

1.3
,
Bayer.

,
1.2.1.1-1.2.1.9,


100%.
pH
( 10 12.5) .
,
, , ,
[1.5].

.

1m.

1.4
.


,
[1.6].

23

1.

.
(Pechiney,
),
,
.
1.4.1
1.4.2.
1.4.1.
1999 ( kt).[1.7]

Pechiney

Aluminium Oxid

Aughinish Alumina

Eurallumina

Alcoa Inespal

British Alcan

Ajka

Tulcea, Oradea

, kt
600
820
710
1550
990
1300
100
300
330, 200
6800

1.4.2.
.[1.1]

Eurallumina , 20% ,
.

.
.

Alcoa Inespal
.



.

Ajka
3-4km

10m.

.

24

1.

, ,


.
1997.

:

2011 ()
113m
3160m
2400m ()

.

1.5
, 70Mt
[1.8].


.

0.7Mt ,


[1.9].

,

25

1.

[1.10].

1.5.1

.
, ,
,
, [1.11-1.17].

, , .

1.5.2

.

, .

Portland [1.181.23]

[1.24-1.29].

1.5.3
(filler).
,


[1.30,1.31].

26

1.

1.5.4


.
(F-), (3-),

(PO4-3),

(As),

(Cr)

(Zn), (Cd), (Cu), (Pb)

(Ni) [1.32-1.40].

1.5.5

.

, ,

[1.411.47].

1.5.6

,
[1.48,1.49]
[1.50-1.53].
2000

(Alcoa,
Alcan, Kaiser). 1.5.1

27

1.

1.5.1. .[1.8]

-
-

SO2
CO2

(. )

(CO2 SO2).

,
.

28

1.

1.6
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pigment from red mud, Cement Concrete Research 27 (1997) 1513
1522.
[1.51] R.E Browner, The use of bauxite waste mud in the treatment of
gold ores, Hydrometallurgy 37 (1995) 339348.
[1.52] S.S Amritphale, A. Anshul, N. Chandra, N. Ramakrishnan, A
novel process for making radiopaque materials using bauxiteRed
mud, Journal of European Ceramic Society 27 (2007) 19451951.

34

1.

[1.53] A. Collazo, D. Fernandez, M. Izquierdo, X.R Novoa, C. Perez,

Evaluation of red mud as surface treatment for carbon steel prior
painting, Progress in Organic Coatings 52 (2005) 351358.

35

2.

, .
,
.

,
~35% .

.
,
2006 .
Fe2O3
Al, Si, Ca Ti, Mg, Na K
.
Cr, Ni, V Cu, Mn Co.
Fe2O3
, AlOOH,
, Al(OH)3, , CaCO3,
, Ca3Al2(SiO4)(OH)8 , CaTiO3
,

Na6Ca2Al6Si6O24(CO3)2.2H2O.

90%
75m. 3.4g/cm3
10m2/g,

.

37

2.

2.1
2.1.1

400g/l,
~69%. ( ,
~3.4g/cm3).
.
) , )

, ) ,
.
,
.

.
,
Na2O
.
20-30% ,
. 1960

.


. ,
100-150kg/h/m2 40-50%.

,
[2.1.1,2.1.2].

38

2.

2-6bar .

1000t/d 120m2.
,

, ,
Na2O.

(high pressure filtering). 2.1.1.1
.
.

.

39

2.

2.1.1.1. .

40

2.

2.1.2



( )
.
2.1.2.1,
. 20
, 180x180mm2
.
200l
30
0.5kW.

2.1.2.1. () , ()
.

. pH
12-13.
5.5bar 380g/l,
.

41

2.

,
1.8g/cm3 35%.

Cu, Ni, V, Co Mn

( 0.5ppm).
,
Na K,

DIN 38414
S4.


.
12% 4%
.

,
.

2.1.3

.
,

42

2.

270 bar, )
4m3/h, ) , , )
,
630x630mm2.
)
, ) , )
. )
( 25%), )

(,

Na2O<3%),

( ),

.
,
.
( ), (30,
40, 50mm), ( :
, : monofilament multifilament).
, ,
(
).
:
,
,
50mm.
350-420g/l
:

27-32%.

43

2.

, 200-300kg/h/m2.

,
520-875 l/h/m2.
,
.

.
2.1.3.1.
.

(g/l)
h.t.m. (kg/h/m2)
(%)

344
301.0
29.1

180
181.0
37.7

,
50mm.
400-500g/l :

26.828.7%.

7086%.

, 170-230kg/h/m2.

,
400-550 l/h/m2.
,

44

2.

200g/l

. 2.1.3.2,
.
2.1.3.2.
.

(g/l)
410
203
2
h.t.m. (kg/h/m ) 206.0 136.0
(%)
26.8
28.7

.

, ,
. 50mm.

150kg/h/m2
.
27% 32%
.
27%

100kg/h/m2. ,
2g/cm3 32%.

2.1.4

2006
,

2628%.

45

2.

.
2.1.4.1.
.

CHOQUENET,

156

760m2

13940L

40mm


()()()
(20m)x(2.9m)x(2.5m)

53t

22h/d

2h/d

, 100bar

24min
-, 1min
-, 5min
-, 4min
-, 3min
-, 1min
-, 10min

55




450g/l

10cst

<350m

2t/m3
350000t/y

2.000.000.
1
. 350.000t ,

.
7.000.000.

46

2.

2.1.4.1-2.1.4.4 ,

,
.

2.1.4.1. .

2.1.4.2.
.

47

2.

2.1.4.3. .

2.1.4.4. .

48

2.

2.2
2.2.1
2.1
40kg
.

,
.

2.2.2

(AA200, Perkin-Elmer, USA)
LiBO2 Analytical methods for
Atomic Absorption Spectroscopy Perkin-Elmer.

.

2.2.2.1 .
2.2.2.1. .

% ..
SiO2
7.37 1.47
Al2O3
18.12 0.93
CaO
15.80 1.73
Fe2O3
41.35 1.70
MgO
0.62 0.22
K2O
0.57 0.30
Na2O
3.81 1.75
TiO2
3.51 1.02
.*
9.05 0.20
*.:

49

2.

Fe2O3 (40-43%.) Al,
Si, Ca Ti, Na, Mg, K.
Co, Cr, Cu, Mn, Ni,
Pb, V, Zn .
2.2.2.2.
Cl-, F- S- .
(751 GPD Titrino,
Metrohm)
196-2.

S- prEN

.
2.2.2.2.
.

mg/Kg
mg/Kg(2)
As
< 0.5
Ba
40
Cd
< 0.1
Cl622(1)
Co
244
Cr
2054
1800
Cu
214
20
F14(1)
Hg
< 0.01
Mn
463
200
Mo
< 0.1
Ni
1052
1000
Pb
101
120
Se
< 0.1
Sn
< 0.2
V
1238
1500
Zn
72
60
(1)
5380
SO3
(1)
, 2)
Laboratories Albhades

(Laboratories Albhades).

50

2.

ICP-MS Hg, Cd, Se, As,

Sn, Mo ICP-OES .

2.2.3

(powder XRD, Philips, PW1830, The
Netherlands). CuK, 30mA 40kV
10 700.

2.2.3.1

1400

1
5

1200

1000

Counts

800

600

1
400

4
6

200

4
3
2 7 2 2

0
10

1
7
4
42 8
7

20

1
4
2 4 3
7

30

1
1

5
2 8
33
7 81

40

50

4 1
35

60

70

2-Theta-Scale

2.2.3.1. XRD , 1.Hematite,

2.Cancrinite, 3.Diaspore, 4.Calcium Aluminum Iron Silicate
Hydroxide,
5.Perovskite,
6.Gibbsite,
7.Potassium
Aluminum
Chromium Oxide hydroxide, 8.Calcite.

(Fe2O3)

(AlOOH) (Al(OH)3)

,
51

2.

(CaCO3)
Bayer
(Ca3Al2(SiO4)(OH)8), (CaTiO3)
(Na6Ca2Al6Si6O24(CO3)2.2H2O)
Bayer.

2.2.4

-laser

diffraction

(Malvern,

Hydro

q3(x), fractional volume distribution, %

x10 (m)

x50 (m)

x90 (m)

0.69

5.32

74.94

100

80

60

40

1
20

0
0.1

10

100

0
1000

Q3(x), cumulative fractional volume undersize, %

2000MU, UK). 2.2.4.1.

Particle size, m

2.2.4.1.

90% 75m

. 2.2.5.

(ASTM D 854-92) 3.4 g/cm3.

52

2.

( BET,
Micromeritics, Gemini 2375) 10m2/g.

2.2.5
<32m,
1m,
.


. EDX
.
2.2.5.1 .
,

( ).

2.2.5.1.
.
(<1m) .

53

2.

>32m 2.2.5.2,

.

2.2.5.2.
63-125m.

2.2.5.3
EDX Al,
Ca Fe.

2.2.5.3.
32 63m. ) , )
.

54

2.

2.2.6

2.2.6.1 1000C.

150C
DTA
TG.

2.2.6.1. DTA-TG
1000C.

200-300C

DTA

, 240C 285C.


.

55

2.

, 324C,
.
[2.2.1,2.2.2]
325-330C. 400C

DTA 500C.
DTA
695C, 731C
750C.
.

, 1000C ,
0.4%,
9.7%.

56

2.

2.2.7
()
,
(IAEA, 1989).
- 70%.

2.2.7.1

,
(), (), ().
2.2.7.1.
.
238U
226Ra
228Ra
228Th
232Th
40K
(Bq/kg)
*
Limits
1000
10000
10000
1000
1000
100000

14932
37943
41931 47223 42723
2111

47045 1500180
455
455
455
47060

46060 1070160
405
405
405
43565

155
2010
102
102
102
30050
*Council Directive 96/29/EUROATOM

228Ra, 228Th

232Th.

238U, 226Ra

40K

40K.

[2.2.3]
.

57

2.

2.3

, .

,
, ,
.
2006

350000t
26-28% 2t/m3.
,
, , Fe2O3
Al, Si, Ca Ti, Mg, Na K
.

(Na

K),

12% 4%
.
, .
Cr, Ni
V,

96/29/EUROATOM.
90%
75m
10m2/g.

58

2.

2.4
[2.1.1] R.F Nunn, Advances in red mud dewatering and disposal
technologies, Light Metals (1998) 107-113.
[2.1.2] N.C.R Oeberg, E.H Steinlechner, Red mud and sands handlingnew thoughts on an old problem, Light Metals (1996) 67-73.
[2.2.1] R.C Mackenzie, Differential Thermal Analysis, Academic Press
Inc. (1970).
[2.2.2] W. Smykatz-Kloss, Differential Thermal Analysis, SpringerVerlag, New York (1974) 185.
[2.2.3] Council Directive 96/29/EURATOM, 13 May 1996, laying down
basic standards for the protection of the health of workers and the
general public against the dangers arising from ionizing radiation.

59

3.

Portland.


( LSF )
, AM SM,
Portland.
,

.
,

42.5N.
(52.5N)
(2 ).
C3S .

,
.

.
2.7%..
(26-28%),

1/3.
27.7MPa
2 51.6MPa 28 .
.

,
.

61

3.

3.1
3.1.1
.

5,600..
3,000..,
.

,
.

, , (CaO,
SiO2, Al2O3 Fe2O3 ).
.

,
. (
>70%), (
>40%) ( >30%).
,

. ,
80%
90m 20% 200m.

Portland ( )
(),
, 3.1.1.1.
,
Portland.

62

3.

3.1.1.1. .

100 CaO
LSF
96.5 98.5
(3.1.1.1)
2.8 SiO2 1.18 Al 2 O3 0.65 Fe2 O3
SiO2
SM
1.2 2.5
(3.1.1.2)
Al 2 O3 Fe2 O3
Al O
AM 2 3
1.8 3.0
(3.1.1.3)
Fe2 O3

3.1.1.1

CaO . 3.1.1.2

.
3.1.1.3 ,
. 3.1.1.2
3.1.1.3
.

3.1.1.1.

63

3.

3.1.1.1. Portland.

64

3.

( 900C)

(
1450oC) .

100C,
() 500C
, CaCO3 CaO,
900C.

>900C. 1200oC

,

(C2S).

, 1250-1280oC,

CaO-Fe2O3-Al2O3

(C3A, C4AF).
1280C ,
Fe2O3 Al2O3,
.
C2S
(C3S)
CaO .

.
/
/ / burnt shale /
/ ( .3).

65

3.

.


.

, ,
[3.1].

( / )

[3.2-3.6],
[3.7, 3.8]
[3.2], iron smelting [3.93.12] (oil shale)
[3.13-3.15].
[3.16],
(rice hush ash) [3.17-3.19],

[3.20,3.21]

[3.22,3.23],

catalyst fines [3.24]

[3.25-3.32],
[3.33-3.35]
[3.36,3.37].

,

66

3.

.


.
,

[3.38,3.39] Portland [3.40,3.41]
.
,
()

Portland.

67

3.

3.1.2

,
.

90m
.
<90m.

3.1.2.1

X (XRD) 3.1.2.1.13.1.2.1.2.
(CaCO3), (SiO2).
2,
2.2.3.1.
(Fe2O3), (AlOOH), (Al(OH)3),
(CaCO3), (Ca3Al2(SiO4)(OH)8),
(CaTiO3) (Na6Ca2Al6Si6O24(CO3)2.2H2O).
.

68

3.

10000

Counts

8000

6000

4000

2000

CC
C

CC

0
20

30

40

50

60

70

2-Theta-Scale

3.1.2.1.1. XRD , C:
(CaCO3), Q: (SiO2), A: (Na(Si3Al)O8).

10000

Counts

8000

6000

4000

Q
Q

Q
2000

Q Q
Q
Q

Q
Q

0
20

30

40

50

60

70

2-Theta-Scale

3.1.2.1.2. XRD , Q: (SiO2).

69

3.

3.1.2.2
3.1.2.2.1
X (XRF).
3.1.2.2.1. .
%

SiO2
7.14
73.53
Al2O3
1.26
15.54
0.93
3.53
Fe2O3
CaO
50.86
2.24
MgO
0.79
0.42
0.16
1.44
K2O
Na2O
0.15
0.31
*

39.00
3.00

100.29
100.01
*.:

. 2
6-8.5% SiO2, 1719% Al2O3, 14-17% CaO 40-43% Fe2O3.

3.1.3
3
, 1%, 3% 5%..
(LSF)
,
(, SM)
( .3).

.

.
,
3.1.3.1.
70

3.

3.1.3.1. .

%.

1%.

3%.

5%.

87.75

86.50

85.30

1.00

3.00

5.00

%
11.25
10.50
9.70

%.
SiO2
14.14
14.66
14.22
13.76
Al2O3
3.28
3.04
3.28
3.52
2.50
1.64
2.47
3.29
Fe2O3
CaO
44.15
44.99
44.57
44.17
MgO
0.69
0.74
0.73
0.72
0.56
0.30
0.29
0.28
K2O
Na2O
0.27
0.20
0.27
0.34
TiO2
0.00
0.04
0.12
0.21
.*
34.45
35.25
34.80
34.50
Total
100.04
100.87
100.76
100.79
a
LSF
97.92
98.44
98.41
98.55
AMb
1.31
1.85
1.33
1.07
c
SM
2.45
3.13
2.47
2.02
*.: ,
% Al 2 O3
100 %CaO
a LSF
,
, b AM
% Fe2 O3
2.8 % SiO2 1.18 % Al2O3 0.65 Fe2O3
% SiO2
c SM
% Al 2 O3 % Fe2 O3

,
Al2O3 Fe2O3
SiO2.
AM SM
. ,

, 3%..

71

3.

3.1.4

laser

DTA-TG

3.1.4.1

3.1.4.1.1
.
95% 90m
100m.

100

80

1%.
3%.
5%.

60

40

20

10

100

(m)

3.1.4.1.1. .

72

3.

3.1.4.2

(DTA DSC) (TGA)
~1000C.

.

. ,

,

.
3.1.4.2.1 DSC-TG
. DSC

270-

280C, .

calcium aluminium iron silicate hydroxide,
( 2).
(~690-700C)
,
880-890C.

TG.
,
1%. (35.14%) 3%.

73

3.

5%.
34.32%.

0.5
100
0.4

1%.
3%.
5%.

90

0.2

80

TG, %

DSC, V/mg

0.3

0.1
70
0.0

-0.1
0

200

400

600

800

60
1000

, C

3.1.4.2.1. , 1%, 3%
5%. .

1450-1550C.
1%.

(ASTM

C114-03).

3.1.4.2.2
.
1%. 1450C
(CaOf) 2.3%, 3 5%.
CaOf<1%.
1550C
0.6%. 3 5%. CaOf <1%
.

74

3.

(SM) (AM)

1%. , .
3%
5%. .

3 5%. 1450C, 1%.
1550C.

1%.
3%.
5%.

1.2

1
0.64

0.64

0
1450

1500

1550
o

3.1.4.2.2. .

3.1.5

<3cm. 110C
1000oC
,
.

75

3.

( MoSi2)
40
min .
,

( 3.1.5.1).

3.1.5.1. .

XRF ( 3.1.5.1.1).
XRD ( 3.1.5.2.13.1.5.2.4) Bogue
( 3.1.4.2.1).

( 3.1.5.3.1).

76

3.

3.1.5.1

.
3.1.5.1.1. .

% .

1% .
3% .
SiO2
22.05
23.61
22.64
Al2O3
5.66
4.17
4.52
3.38
1.94
3.17
Fe2O3
CaO
67.12
67.45
66.93
MgO
1.60
0.83
0.82
0.54
0.24
0.32
K2O
Na2O
0.23
0.17
0.27
SO3
0.22
0.08
0.13

100.80
98.49
98.80

5% .
21.53
4.89
4.40
66.07
0.81
0.38
0.38
0.16
98.62

,
Fe2O3 Al2O3 CaO SiO2 .

3.1.5.2.

3.1.5.2.1-3.1.5.2.4, ,
Bogue,
3.1.5.2.1.
XRD

,
Portland
(C3S), (C2S),
(C3A) (C4AF).

Bogue, ,
C4AF

77

3.

(C2S) (C3A).
(C3S) 62-66% .
,
1%. 5%.
C4AF.

Bogue 6% 13%

3.1.5.2.2 3.1.5.2.4.

3.1.5.2.1. .

% .

1% .
3% .
5% .
% C3S*
62
64
65
66
*
% - C2S
16
19
16
12
% C3A*
9
8
7
6
*
% C4AF
10
6
10
13
*

Bogue ( .3)

1600

1,2

1400
1200

Counts

1000

1,2
1

800
600

400

1
200

4 1

1
3
4

1
1
3

4 14

1
1
4

1,3
1 1,4

3 4 1

0
10

20

30

40

50

60

2-Theta-Scale

3.1.5.2.1. XRD , (1) Calcium

Silicate (C3S), (2) Calcium Silicate (C2S), (3) Aluminum Calcium Oxide
(C3A), (4) Brownmillerite (C4AF).

78

3.

1600

1,2

1400
1200

1,2

Counts

1000

800
600

400

200

1 1
3
4

1
3
4

1
3

1
1

1,3
1 1,4

1
1

0
10

20

30

40

50

60

2-Theta-Scale

3.1.5.2.2. XRD 1%. ,

(1) Calcium Silicate (C3S), (2) Calcium Silicate (C2S), (3) Aluminum
Calcium Oxide (C3A), (4) Brownmillerite (C4AF).

1600

1,2

1400
1200

Counts

1000

1,2
1

800
600

400

1
200

4 1

1
3
4

1
1
3

4 14

1
1
4

1,3
1 1,4

3 4 1

0
10

20

30

40

50

60

2-Theta-Scale

3.1.5.2.3. XRD 3%. ,

(1) Calcium Silicate (C3S), (2) Calcium Silicate (C2S), (3) Aluminum
Calcium Oxide (C3A), (4) Brownmillerite (C4AF).

79

3.

1600

1,2

1400
1200

1,2

Counts

1000

800
600

1
400

200

4 1
1

1
3 4 14

1
3
4

1
1
3

1
4

1,3
1 1,4

1
3 4

1
1

0
10

20

30

40

50

60

2-Theta-Scale

3.1.5.2.4. XRD 5%. ,

(1) Calcium Silicate (C3S), (2) Calcium Silicate (C2S), (3) Aluminum
Calcium Oxide (C3A), (4) Brownmillerite (C4AF).

80

3.

3.1.5.3

.
(C3S)
(C2S).
(C3A) (C4AF)

3%. .

.

( ).

lamellas

.
(clusters).
.
,
,
.

.

81

3.

3.1.5.3.1. (a)
C3S, C2S, (b)
C3S ( ) , (c)
C3S, C2S, (d)
C3S, , (e)
C3S, C2S, (f)
C3S, , (g)
C3S , (h)
C2S, .

82

3.

3.1.6
, 5%.
Portland CEM I

. (Blaine)
EN 196-6,
196-3 ( 3.1.6.1).
2, 7, 28, 90, 180 360
EN 196-1, ( 3.1.6.2, 3.1.6.1, 3.1.6.2).
3.1.6.1,

.

,

80 100
140-160 .


Portland .
3.1.6.1. .

1% . 3% . 5% .

3730
3810
4010
3870
(min)
100
100
80
90
(min)
160
140
160
150

21.6
22.4
22.6
22.2
2, 7, 28, 90, 180 360 ,
42.5N
EN 196 ( .3). ,

83

3.

52.5N ( .3)
2 20MPa.

C3S [3.1].

3.1.6.2. .

(MPa)

1%.
3%.
2
19.2
26.5
27.4
7
39.2
48.2
42.9
28
55.6
62.9
57.5
90
57.5
69.6
65.2
180
60.2
71.2
67.8
360
64.3
73.1
69.8

5%.
30.8
44.3
58.4
63.0
68.3
70.2

, (360
),

3.1.6.1 3.1.6.2.

3.1.6.1. 28 .

84

3.

3.1.6.2. (360 )
.

85

3.

3.1.7

,
.

. ,


+III +VI . ,

.

6.
2
0.2%.

.
3.1.7.1.
3.1.7.1.
.

LSF
AM
SM

%.

100.00
96.21
1.31
2.45

1%.
97.80
1.20
1.00
96.12
1.34
2.42

2%.
55.00
35.00
2.00
8.00
96.30
1.22
2.25

3%.
55.00
34.50
3.00
7.50
96.32
1.20
2.19
86

3.

LSF,

AM,

SM

3.1.5
.

Lithium Metaborate Fusion [4.42]
.
(1450C)
.
XRF
Bogue (
.3.2). 3.1.7.2.
3.1.7.2. .
%.

1%.
2%.
3%.
SiO2
21.82
21.45
21.53
21.00
Al2O3
5.56
5.72
5.61
6.13
Fe2O3
4.12
4.71
4.07
4.77
CaO
67.37
66.87
66.34
66.38
MgO
1.07
1.07
1.35
1.37
K2O
1.16
1.14
0.84
0.87
Na2O
0.25
0.31
0.29
0.36

101.35
101.31
100.17
101.08

%.

%C3S*
65
64
63
63
% - C2S*
13
13
14
13
*
%C3A
8
7
8
8
%C4AF*
13
14
12
14
* Bogue ( .3)

, C3S 63-65%, C2S 13-14%, C3A 7-

87

3.

8% C4AF 12-14%. 5%.

Portland.
15 ,

.
3.1.7.3.
3.1.7.3.
.
Cr

1%
2%
3%

0.153
0.187
0.229
0.271
(mg/g)

0.053
0.066
0.072
0.086
(mg/g)
%
35
35
32
32

0.153mg/g
0.271mg/g 3%..

0.053mg/g 0.086mg/g. ,
(32-35% )
1 2%. .

88

3.

3.2
3.2.1
,
.


.
.

Portland 42.5N.
7 28 .

3.2.2

,

,
.
20-28% , 3.2.2.1.
3.2.2.1. .

% .
SiO2
6.53
Al2O3
21.67
Fe2O3
41.57
CaO
10.97
MgO
0.26
K2O
0.12
Na2O
2.92
TiO2
5.07
SO3
0.56
Cr2O3
0.30
.*
9.98

99.95
*.:
89

3.

3.2.3 ()
0.8-2.7%.
6
.
3.2.3.1. .


1
2
3
4
5
% .
%
87.85 87.80
87.66
87.50
87.34
%
10.36 10.61
10.54
10.46
10.38
%
1.23
0.79
0.63
0.46
0.28
%
0.56
%
0.79
1.17
1.58
2.00

% .
SiO2
13.95 14.04
13.99
13.95
13.90
Al2O3
3.21
3.10
3.15
3.21
3.27
2.72
2.63
2.67
2.72
2.77
Fe2O3
CaO
43.38 43.45
43.42
43.38
43.35
LSF
97.26 97.25
97.26
97.25
97.25
SM
2.35
2.45
2.40
2.35
2.30
AM
1.18
1.18
1.18
1.18
1.18

ppm
Cr
6
13
19
25
32
Mn
75
49
40
31
21
Pb
86
56
45
34
22
Zn
123
79
64
47
29
Cu
62
40
32
24
15

6
87.02
10.26
2.72
13.82
3.38
2.88
43.28
97.14
2.21
1.17
43
5
3
1
1

,
2.72%

.
,

(Mn), (Pb), (Zn)
(Cu) (Cr).

90

3.

(87.0-87.8% 10.3-10.6% )
,
Mn, Pb, Zn Cu Cr
.

3.2.4
,
500 .
.


. ,
,
.


.

1/3 (/)
,
.

.

3.2.5

XRF
Bogue.
3.2.5.1.

91

3.

3.2.5.1. .

1
2
3
4
5
%.
SiO2
22.04
22.18
22.10
22.04
21.96
Al2O3
5.49
5.30
5.39
5.49
5.59
3.51
3.39
3.44
3.50
3.57
Fe2O3
CaO
65.94
66.04
65.99
65.94
65.89

%.

C3S
59.05
59.83
59.55
59.04
58.68
C2S
18.64
18.46
18.43
18.65
18.69
8.63
8.31
8.46
8.61
8.77
C3A
C4AF
10.65
10.32
10.47
10.68
10.86

6
21.84
5.77
3.72
65.79
57.79
18.99
9.04
11.29

Fe2O3
Al2O3 CaO SiO2.

. ,

(C3A)

(C4AF)
, (C3S, C2S) .

58-60% C3S, 1819% C2S, 8-9% C3A 10-11% C4AF 59% C3S,
18.6% C2S, 8.6% C3A 10.7% C4AF .

3.2.6

Portland
CEM I 42.5.

. 2 28

92

3.

3.2.6.1
EN.
3.2.6.1. 2 28
.
(MPa)
CEM I 42.5N
CEM I 42.5N
( EN196)
( )
2
10.0
26.2 - 27.7
28
42.5
49.3 - 51.6

42.5N EN196.

93

3.

3.3
(
/ ) 5%.,
,
.
/
.

( Fe2O3),
.
( 90% <75m)

.
.

,
Mn, Pb, Zn Cu .

Cr

,
, Cr.
/

.

2-3%..

~15Mt/y 21Mt ,

94

3.

2-3% 400600Kt 700Kt

, ,

XRD.
( , , )


EN.
,
42.5 ( Portland). ,


52.5( .3).

42.5

Portland).

26.227.7Pa 2 49.3-51.6 Pa 28 .



,

.
,

. ,
,

95

3.

.
1/3
.

,
.

96

3.

.3

.3.1. 197-1.

CEM I

95-100

CEM II

II/A-S
II/B-S
II/A-D
II/A-P
II/B-P
II/A-Q
II/B-Q
II/A-V
II/B-V
II/A-W
II/B-W
II/A-T
II/B-T
II/A-L
II/B-L
II/A-M
II/B-M

80-94
65-79
90-94
80-90
65-79
80-94
65-79
80-94
65-79
80-94
65-79
80-94
65-79
80-94
65-79
80-94
65-79

6-20
21-35
-

CEM III

II/A
II/B
II/C

35-64
20-34
5-19

36-65
66-80
81-95

CEM IV

IV/A
IV/B

65-89
45-64

CEM V

V/A
V/B

40-64
20-39

18-30
31-50

P
Q
V
Portland*
Portland
6-10
6-20
21-35
6-20
21-35
6-20
21-35

11-35
36-55

16-30
31-50
D

0-5

6-20
21-35
-

6-20
21-35
-

6-20
21-35

0-5
0-5
0-5
0-5
0-5
0-5
0-5
0-5
0-5
0-5
0-5
0-5
0-5
0-5
0-5
0-5
0-5

0-5
0-5
0-5

0-5
0-5

0-5
0-5

K: , S: , P Q: , V W: ,
T: Burnt Shale, L: , D: (Silica),
: ()

.3.2. Bogue
.
%C4AF = 3.043(%Fe2O3)
%C3A = 2.650(%Al2O3) 1.692(%Fe2O3)
%C3S = 4.071(%CaO) 7.600(%SiO2) 6.718(%Al2O3) 1.43(%Fe2O3)
%C2S = 2.867(%SiO2) 0.754(%C3S)

97

3.

.3.3.
, European Standards.
(MPa)

2 days
7 days
28 days
32.5N
16.0
32.552.5
32.5R
10.0
42.5N
10.0
42.5-62.5
42.5 R
20.0
52.5N
20.0
52.5
52.5 R
30.0
-

98

3.

3.4
[3.1] J.I. Bhatty, F.M. Miller, S.H. Kosmatka, Innovations in Portland
Cement Manufacturing, first ed., Porland Cement Association, Skokie,
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[3.2]

S.C

Ahluwalia,

C.H

Page,

Effect

of

Low

Grade

Fuels,

Combustibles and Non-Traditional Raw Materials, 9th International

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[3.3] S.C Ahluwalia, S. Laxmi, S.K Chopra, High Magnesia and
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Dry Conversion, First NCR International Seminar on Cement and
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99

3.

[3.8] G.L Young, G.L Morrison, Passamaquoddy Technology Recovery

Scrubber at the Dragon Product Company, Inc Cement Plant, Rock
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[3.9] R.D Young, Method and Apparatus for Using Blast Furnace Slag
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[3.12] I.S Valkova, R.G Dogandzhieva, Producing Portland Cement
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[3.13] L.S Freiman, M.W Kougija, Residues from Oil Shale Processing
Used

as

Cement

Material,

Zement-Kalk-Gips,

Bauverlg

GMBH/Mavlean Hunter, Wiesbaden, Germany, vol.50 (1997) 44-49.

[3.14] R. Rohrbach, Production of Oil Shale Cement and Recovery of
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[3.15] H. Rechmeier, The five stage preheater kiln for burning of
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100

3.

[3.16] J.I Bhatty, Role of Trace Element on Cement Manufacture and

Use A Laboratory Study, Porland Cement Association, Skokie,
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Fuel

and

Raw

Material

Component

Respectively

in

Cement

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Delhi, India, vol.II (1992) 224-231.
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cement

and

concrete,

Resources,

Conservation

and

Recycling,

doi:10.1016/j.resconrec.2008.06.008
[3.22] Guohua Chena, Harry Leea, King Lun Younga, Po Lock Yuea,
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101

3.

[3.24] J.I Bhatty, J. Gajda, F.M Miller, Use of High Carbon Fly Ash in
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Ash as a Raw Material Component, Zement-Kalk-Gips Bauverlg
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Sozai, Japan, vol.107(2) (1991) 85-91.
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Conservation of Raw Material Through Use of Industrial Wastes in
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102

3.

[3.33]

Pai-Haung

Shiha,

Juu-En

Changa,

Li-Choung

Chiang,

Replacement of raw mix in cement production by municipal solid

waste incineration ash, Cement and Concrete Research 33 (2003)
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[3.34] P. Krammart, S. Tangtermsirikul, Properties of cement made by
partially replacing cement raw materials with municipal solid waste
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and

calcium

carbide

waste,

Construction

and

Building

Materials 18 (2004) 579583.

[3.35] Nabajyoti Saikia, Shigeru Kato, Toshinori Kojima, Production of
cement clinkers from municipal solid waste incineration (MSWI) fly
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(1997) 1037-1046.
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Addition in the Raw Meal for the Production of Portland Cement
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103

3.

[3.42] Analytical Methods for Atomic Absorption Spectroscopy, GC-4R

- Analysis of Silicates and Carbonates: Lithium Metaborate Fusion
Procedure, Perkin-Elmer Corporation, Manual part No. 0303-0152,
Release D (1996) 236-237.

104

4.

2%.

(service

life)

(second

life).

, NEN 7345-tank test
prEN 14429-pH dependence test
. ,
,
Cr, Ni V .

, Cr

(4.5mg/m2 4.2mg/m2 )
Ni V
.

.
()

. pH 11
Cr 0.8mg/l 1.8 mg/l
, pH 4 Cr 1.6mg/l
2.3mg/l .
Ni, V
.

105

4.

4.1

[4.1,4.2]

.

.
,
,
[4.3].
,

[4.4].
,
,
, ( 4.1.1).

4.1.1.
.[4.4]

106

4.

,
,
(leaching tests) [4.5].

,
[4.6].

[4.7].

.

[4.8].
1. :
()
/ .
/, pH
, ,
.
2. :

.
3. :
.

.


107

4.

. ,

,
,

.
4.1.1.
.[4.3]

Tank test

Tank test

Column test,
compacted
granular test

pH,
pH-static leach

test

,

,
(),
,
,
( ,

108

4.

,
), (
) [4.9].

.

.
4.1.2.
.[4.9]

,
As

,

Cd

,
Co

, ,

Cr
,

,


Cu

,

Ni

,
,

,
Pb
,

,

Sn

Tl

Zn

109

4.

,
2, Cr, V Ni.

.

( )
( ).

110

4.

4.2


. 2%
, .
4.2.1
4.2.1. .

SiO2
Al2O3
Fe2O3
CaO
MgO
TiO2
K2O
Na2O

LSF
AM
SM
*

%.

2%.
100.0
55.0
0.0
2.0
0.0
35.0
0.0
8.0
100.0
100.0
%.
13.70
13.70
3.49
3.60
2.59
2.59
42.30
42.24
0.67
0.86
*
0.10
0.73
0.53
0.16
0.21
37.00
36.50
95.63
95.22
1.35
1.39
2.25
2.21

,
,
.
,
10000C CO2,
.

111

4.

, 40 min 1450

0C

.
XRF

Bogue. Cr,
Ni V .
,
4.2.2.
4.2.2. .
% .

2%.
SiO2
21.82
21.53
Al2O3
5.56
5.61
4.12
4.07
Fe2O3
CaO
67.37
66.34

% .
C3S*
65
63
*
C2S
13
14
C3A*
8
8
*
13
12
C4AF

mg/g
Cr
0.277
0.387
Ni
0.106
0.134
V
0.201
0.290
* Bogue ( .3.2)

XRD,
4.2.1,

.
Cr, Ni, V

. 26%

112

4.

Ni 44% V.
38%.

2000

1,2

1800

1600

1,2

1
1400

Counts

1200

2%.

1000

1
800

2 11

34

1
4

1,3

600
400
200

0
10

20

30

40

50

2-Theta-Scale

4.2.1. XRD , (1) Calcium

Silicate (C3S), (2) Calcium Silicate (C2S), (3) Aluminum Calcium Oxide
(C3A), (4) Brownmillerite (C4AF).

, 5%.
10 ,

Portland

CEM

I,

113

4.

4.3
4.3.1

EN

196-1

[4.10].

4x4x16cm,

, 4.3.1.1.

4.3.1.1. .

28 . 28
. ,
4x4x6cm, NEN 7375 [4.11],
,

4x4x10cm, prEN 14429

[4.12].

114

4.

4.3.2



. 64 .
, .
,
,
.
(0.25, 1, 2.25, 4, 9, 16, 36, 64 )
.
,

. , pH .
, ( 2%. )

,
.
64
Cr, Ni V.

, ,
.
4.3.2.1 - 4.3.2.3 C
(mg/l)
*i
(mg/m2).

0.013m2 .

115

4.

E *i

Ci V
f A

(4.3.2.1)

:
Ci, Cr, Ni V i g/l, i=1-8
V, l
A, m2
f, : 1000g/mg
4.3.2.1. NEN 7345
Cr.

2%.
()
CCr (mg/l) *i (mg/m2) CCr (mg/l) *i (mg/m2)
0,25
0.020
0.332
0.016
0.258
1
0.052
0.858
0.043
0.699
2,25
0.049
0.805
0.037
0.596
4
0.023
0.374
0.015
0.246
9
0.025
0.416
0.025
0.407
16
0.031
0.507
0.039
0.631
36
0.028
0.462
0.035
0.560
64
0.046
0.755
0.050
0.811
4.3.2.2. NEN 7345
Ni.

2%.
()
CNi (mg/l) *i (mg/m2) CNi (mg/l) *i (mg/m2)
0,25
BDL*
BDL*
1
BDL*
BDL*
*
*
BDL
2,25
BDL
*
*
4
BDL
BDL
*
*
9
BDL
BDL
*
*
16
BDL
BDL
*
*
BDL
36
BDL
*
*
64
BDL
BDL
* BDL:

116

4.

4.3.2.3. NEN 7345

V.

2%.
()
*
2
CV (mg/l) i (mg/m )
CV (mg/l)
*i (mg/m2)
0,25
BDL*
BDL*
1
BDL*
BDL*
*
*
2,25
BDL
BDL
4
BDL*
BDL*
*
*
9
BDL
BDL
16
BDL*
BDL*
*
*
36
BDL
BDL
64
BDL*
BDL*
* BDL:

Cr. Ni
V
,
. Cr

(mg/m )

2%.

0
0

10

20

30

40

50

60

()

4.3.2.1.
.

117

4.

2%.
64 . ,
4.5mg/m2
4.2mg/m2.

,
.

,
8
.

(logn)

(logt).
logn logt
(rc)
(sd) .

.

0.35 0.65
0.5.

.5

.
, 9 64 .
,

( .5), 64

118

4.

.
,
.

119

4.

4.3.3

pH

. 48

pH 4
0.3 .
,
10 ( / 10:1).

pH
.
.
48
, ,

8 pH
4-12.
, ( 2%. )
1mm.

20g

8 pH
4-12.

pH ,
(HNO3 5M) .

120

4.

, pH
4, 6, 6.5, 8, 9, 10.5, 11, 12.5.

.
48

Cr, Ni V.

.
4.3.3.1. pH.

2%.
pH
Cr (mg/L)
4
1.579
2.278
6
1.550
2.220
6.5
1.453
2.200
8
1.361
2.189
9
1.138
2.062
10.5
1.045
1.798
11
0.771
1.768
12.5
0.000
0.022
Ni (mg/L)
4
1.555
2.074
6
1.264
1.605
6.5
1.107
1.218
8
0.509
0.730
9
0.358
0.339
10.5
0.333
0.307
11
0.242
0.271
12.5
0.002
0.000
V (mg/L)
*
4
BDL
BDL*
*
6
BDL
BDL*
6.5
BDL*
BDL*
8
BDL*
BDL*
*
9
BDL
BDL*
10.5
BDL*
BDL*
*
11
BDL
BDL*
12.5
BDL*
BDL*
* BDL:

121

4.

4.3.3.1
4.3.3.2.

Cr (mg/l)

10

2%.

0.1

0.01
4

10

12

14

pH

4.3.3.1. pH Cr
.

Ni (mg/l)

10

2%.

0.1

0.01
4

10

12

14

pH

4.3.3.2. pH Ni
.

122

4.

Cr Ni
pH . ,
Cr Ni
.
Ni. V
.
,
Cr pH
.

.


Cr (0.387mg/g
0.277mg/g ).
Ni

pH9. pH<8

. Ni
4<pH<8
.
Ni

Ni
(0.106mg/g , 0.134mg/g 2%. ).

123

4.

4.4
2%.
,
0.277mg/g 0.387mg/g (
38%), Ni 0.106 mg/g 0.134 mg/g
( 26%), V 0.201 mg/g 0.290
mg/g ( 44%).


Bogue X,
.

.


NEN 7375-Tank test

prEN 14429-pH dependence test.

Cr,
Ni, V ,
. Ni
V
Cr 64
(4.5mg/m2
4.2mg/m2 ).
Cr
,

124

4.

( 4.3.2.1)
.

Cr
2%.
9-64.
pH
Cr Ni

.
,

.

Cr Ni.

125

4.

.4

.
1. derived cumulative leaching

n Ei * t i

t i t i 1 , mg/m2 n=1-8

(A.4.1)

:
*i, Cr/Ni/V mg/m2
ti, s
ti-1, s
i 1 8.

()
21600
86400
194400
345600
777600
1382400
3110400
5529600

*i (mg/m2)
n (mg/m2)
0.332
0.332
0.858
1.717
0.805
2.415
0.374
1.494
0.416
1.248
0.507
2.028
0.462
1.385
0.755
3.021

2%.
*i (mg/m2)
n (mg/m2)
0.258
0.258
0.699
1.399
0.596
1.787
0.246
0.984
0.407
1.221
0.631
2.524
0.560
1.680
0.811
3.246

2.

1
2
3
4
5
6

2-7 ()
5-8 ()
4-7 ()
3-6 ()
2-5 ()
1-4 ()

126

4.

3. (concentration factor,
CF*) .


.
log(n) log(ti),

(linear

regression)

(rc) (sd) .

1

2
1

n (mg/m )

n (mg/m )

0.1

0.1

0.01

0.01

0.1

10

0.1

100

10

100

4
1

n (mg/m )

n (mg/m )

()

()

0.1

0.01

0.1

0.01

0.1

10

100

0.1

()

10

100

()

6
1

n (mg/m )

n (mg/m )

0.1

0.1

0.01

0.01

0.1

()

10

100

0.1

10

100

()

127

4.

2%.
1

n (mg/m )

n (mg/m )

0.1

0.01

0.1

0.01

0.1

10

100

0.1

()

n (mg/m )

n (mg/m )

100

0.1

0.01

0.1

0.01

0.1

10

100

0.1

()

10

100

()

6
1

n (mg/m )

n (mg/m )

10

()

0.1

0.1

0.01

0.01

0.1

10

0.1

100

10

100

()

()

1
2
3
4
5
6

CF
17
16
13
15
18
18

rc
-0.07
0.36
0.02
-0.11
-0.19
0.61

sd
0.11
0.16
0.11
0.15
0.12
0.26

CF
16
19
14
15
15
14

2%.
rc
0.09
0.36
0.31
0.19
-0.12
0.56

sd
0.15
0.16
0.16
0.20
0.12
0.29

128

4.

4. ,

.

1
2
3
4
5
6

0.35

Depletion
Depletion
Depletion
Depletion

(rc)
> 0.35 0.65

> 0.65

5.

CF 1.5

sd 0.5

0.35 < rc 0.65

6. ,
64

1

64

b
1b a
E *i
64

i a t i t i 1

(A.4.2)

5-8 ( 9 64)
,

129

4.

b
1b a
E *i
=

i a ti ti 1

U i

E *i
t i t i 1

(U 5 U 6 U 7 U 8 ) 4

(A.4.3)

, i=5-8

64 * i *

(A.4.4)

*i, Cr/Ni/V
mg/m2
7. (A.4.4)
(A.4.2)
3-6 4-7 0.35,
(A.4.4)
.

7, .

64
*
64

(mg/m2)

2%.
2.945
3.306
4.509
4.209

8.

,
.

130

4.

.4

prEN 14429.
.4.1. .

1
2
3
4
5

20
20
20
20
20
(g)

7
8.3
9
11
(ml)

5
5
5
5
5
(mol/l)

200
195
190
190 185
(ml)

/
10
~10
~10
~10 ~10
(l/Kg)
pH 4
12.50 11.00 6.90 7.11 6.38
pH 44
12.54 11.06 10.56 8.98 8.10
pH 48
12.52 11.02 10.52 8.98 8.13
pH (4-44)
0.04
0.06
3.66 1.87 1.72
pH (44-48) 0.02
0.04
0.04 0.00 0.03

.4.2. 2%. .

1
2
3
4
5

20
20
20
20
20
(g)

7
8.3
9
11
(ml)

5
5
5
5
5
(mol/l)

200
195
190
190 185
(ml)

/
10
~10
~10
~10 ~10
(l/Kg)
pH 4
12.45 10.60 7.20 7.45 6.43
pH 44
12.56 10.98 10.48 9.09 8.10
pH 48
12.53 10.96 10.52 9.01 8.19
pH (4-44)
0.11
0.38
3.28 1.64 1.67
pH (44-48) 0.03
0.04
0.04 0.08 0.09

20

20

20

12

13

15

185

185

185

~10

~10

10

4.06
6.50
6.51
1.94
0.01

3.78
6.02
6.06
2.24
0.04

3.25
4.05
4.03
0.80
0.02

20

20

20

12

13

15

185

185

185

~10

~10

10

4.30
6.58
6.57
2.28
0.01

3.71
6.02
6.13
1.31
0.11

3.28
3.99
3.99
0.71
0.00

131

4.

4.5
[4.1] E.K Mantus, K. Kelly, G.A. Pascoe, All Fired Up-Burning
Hazardous

Waste

in

Cement

Kilns,

Environmental

Toxicology

International, Seattle, WA, 1992.

[4.2] K.H Karstensen, Burning of hazardous waste as co-fuel in a
cement kiln-does it affect the environmental quality of cement?, in:
J.J.J.M. van der Sloot, H.A. van der Sloot, Th.G. Aalbers (Eds.),
Environmental Aspects of Construction with Waste Materials, Stud
Environ Sci vol. 60, Elsevier, Amsterdam, 1994, pp. 433-452.
[4.3] H.A van der Sloot, D.S. Kosson, A unified approach for the
judgement of environmental properties of construction materials
(Cement-based, asphaltic, unbound aggregates, soil) in different
stages of their life cycle.
[4.4] H.A. van der Sloot, J.J Dijkstra, Development of horizontally
standarized leaching tests for construction materials: A material
based or release based approach? Identical leaching mechanisms for
different materials.
[4.5] H.A van der Sloot, Comparison of the characteristic leaching
behaviour of cements using standard (EN 196-1) cement mortar and
an assessment of their long-term environmental behaviour in
construction products during service life and recycling.
[4.6] A.G Kim, Coal-combustion byproducts: Survey of Methods and
Results, National Energy Technology Laboratory, U.S Department of
Energy, Pittsburgh, Pennsylvania, 2001.
[4.7] H.A van der Sloot et al., Harmonisation of leaching/extraction
test, 1997.

132

4.

[4.8] Leaching behaviour tests-influence of pH on leaching with initial

acid/base addition-Horizontal standard.
[4.9] Heavy Metals in Cement and Concrete Resulting from the Coincineration of Wastes in Cement Kilns with Regard to the Legitimacy
of Waste Utilisation.
[4.10] EN 196-1, Methods of testing cement determination of
compressive strength.
[4.11] EA NEN 7375:2004, Leaching characteristics of moulded or
monolithic building and waste materials. Determination of leaching of
inorganic components with the diffusion test, version 1.0, April 2005.
[4.12] prEN 14429 Leaching behaviour tests-Influence of pH on
leaching with acid/base addition-Horizontal standard.

133

5.

.
Portland

(C3S)

(~1350C)
.


Portland
.

4CaO.3Al2O3.SO3 .

5.1
5%
CO2 [5.1].

,

CO2.
,
1kg Portland ( )
3000kJ. , 2000kJ

3, 1000kJ
[5.2].


(LSF), 5.1.1.
135

5.

LSF

100%CaO
2.8% SiO2 1.18% Al 2 O3 0.65% Fe2 O3

(5.1.1)

80 100%,
Portland, 1570
1800kJ/kg [5.3].

CO2
.

1kg

1.2Kg

2930kJ .

CO2

0.53Kg

CaCO3 CaO CO2

100 = 56 + 44,

(44/100)x1.2 = 0.53Kg

C 0.32Kg

C O2 CO2

12 + 32 = 44,

(44/12)(2930/32792) = 0.32Kg

,
[5.4].

.

CaCO3,
CO2
136

5.

.
LSF
.

20 [5.5].
Portland

(C2S)

(C3S).
C2S C3S
LSF 75%,

[5.6]. C3S
>1300oC C2S
>1000oC
[5.3].

12% [5.2]
6-10% [5.7,5.8] CO2

.
,
( 7 ) C2S
C3S.
.
(
>500oC/min)

700-1300oC

C2S (- )
,
[5.9].
Klein (4CaO.3Al2O3.SO3).

137

5.

Klein
SO3
.

CaO-SiO2-Al2O3

CaO-SiO2-Al2O3 SO3
CaO-SiO2-Al2O3 CaO-SiO2-SO3 [2]
.

C2S, C4A3 S C S
1350oC

[5.10,5.11]

C2S,

C3S,

C3A

CaO-SiO2-Al2O3 .

Fe2O3 C4AF
[5.12].

Klein - Al2O3 Fe2O3
,
third series cements [5.13,5.14].

.



- .

C4A3 S .

.

138

5.

5.2

, , ,
(AYK), ().
3

,
90m
.

5.2.1

XRF
5.2.1.1
5.2.1.1. .
%

SiO2
70.85
12.76
14.30
0.20
Al2O3
18.03
0.18
49.20
0.10
3.70
0.04
23.00
0.07
Fe2O3
CaO
1.59
24.73
3.62
53.00
MgO
0.57
1.85
**
1.30
**
**
1.72

0.05
K2O
Na2O
0.41
**
**
**
**
**

39.30

**
SO3
.*
4.18
23.14
10.00
45.20

101.05
101.00
100.12
99.92
**
*.: , :

X (XRD) 5.2.1.15.2.1.4.

139

5.

5000

Q
4000

Counts

3000

2000

Q Q
Q
Q

Q
Q

1000

0
20

30

40

50

60

70

2-Theta-Scale

5.2.1.1. XRD , Q: (SiO2), A:

(Na(Si3Al)O8).

5000

4000

Counts

G
3000

2000

G,D
G
G G
G
G
G
G
G G
GG
G
G
G
Q
G D

1000

G
G
G

0
10

20

30

40

50

60

70

2-Theta-Scale

5.2.1.2. XRD , G: (CaSO4.2H2O), Q:

(SiO2), D: (CaMg(CO3)2).

140

5.

3500

D
D

3000

Counts

2500

D B
D
D

2000

D,H
H

B H

40

50

D
H
D,H
D
D
D
D D
D
B

D
1500

D
B
H

1000
500
0
10

20

30

60

70

2-Theta-Scale

5.2.1.3. XRD , D: (AlO(OH)),

B: (Al2(OOH)2), H: (Fe2O3).

16000

C
14000
12000

Counts

10000
8000
6000
4000
2000

C
C
C

C
C

0
10

20

30

40

50

60

70

2-Theta-Scale

5.2.1.4. XRD AYK, C: (CaCO3).

3 2 .

141

5.

.
,

(<15). , ,
, ,
, (AYK),
.

5.3


3 LSF,
AM SM.

Portland
.
.


. (BC),
C-S-F-A,
1350oC C2S, C3A C4AF.
- (BSFC1

BSFC2), C-S-F-A- S ,

C4AF, C4A3 S ,

C S C2S.

142

5.

.
Bogue
C-S-F-A 1450oC ( A.5)
( .5 .5).
( , BC)
(C2S) >70%
(C4AF)

>12%

Portland)

Portland ( 2-3%.). (

BSFC1

BSFC2)

C4AF


.
C2S 40-50%.
,

Bogue 5.3.1.
5.3.1. .
BC
BSFC1

%.
C3S
C2S
73
49
9
C3A
C4AF
18
23

C4A3 S

CS

SiO2
Al2O3
Fe2O3
CaO
SO3

BSFC2
42
37

14

18

14

26.17
7.22
5.90
60.71
100.00

%.
17.15
11.71
7.63
54.18
9.33
100.00

14.71
16.65
12.25
44.78
11.62
100.00

143

5.

,

.

Excel.

0.5%
( .5).

5.3.2.

5.3.2. .
%.

BC
BSFC1
%
82.80
70.00
%
4.20
2.00
%
13.00
%YK
%
16.00
%
12.00

BSFC2
38.00
8.00
14.20
20.80
19.00

BSFC1,
C4AF,

5.4

.
BC
1330oC BSFC1 BSFC2
1280oC 1300oC .

144

5.

Portland 120 150oC.

.

.

5.5

. (BC) 5%. ,
(BSFC1 BSFC2) ,
. 10
. XRD,
5.6.1-5.6.3, .
(Blaine) EN
196-6,
196-3 ( 5.5.1). 2, 7 28
EN 196-1
5.6.2.

145

5.

5.6
5.6.1-5.6.3,
.
BC
C2S C4AF C3A

C3S
,
1330oC.

BSFC C2S, C4AF, C S

Klein Yeelimite (C4A3 S ),

[5.15,5.16]
.

700

1
600
500

Counts

400
300

200

4
1 3
2

100

1
4 34

4
1

2 4
3

0
10

20

30

40

50

60

70

2-Theta-Scale

5.6.1. XRD BC, (1) Calcium Silicate

(C2S), (2) Brownmillerite (C4AF), (3) Aluminum Calcium Oxide (C3A),
(4) Calcium Silicate (C3S), (5) Gypsum (CaSO4.2H2O).

146

5.

1000
900
800
700

Counts

600
500

1,2 2

400

1
2

300
200

2
2

100

3
1 4

22 2

1
1
2 1 2

4 11
1

0
10

20

30

40

50

60

70

2-Theta-Scale

5.6.2. XRD BSFC1, (1) Calcium Silicate

(C2S), (2) Brownmillerite (C4AF), (3) Anhydrite (C S ), (4) Yeelimite

(C4A3 S ).

1000

900
800
700

Counts

600

1,2

500

4
2
2

400
300
200

13 4

2
2

1
1

2 2

11

1
4 1 4
2

11

100
0
10

20

30

40

50

60

70

2-Theta-Scale

5.6.3. XRD BSFC2, (1) Calcium Silicate

(C2S), (2) Brownmillerite (C4AF), (3) Anhydrite (C S ), (4) Yeelimite

(C4A3 S ).

147

5.

1, 2, 7 28 .
5.6.1. .

BC
BSFC1
BSFC2
2
(cm /g)
4100
4850
4430
(min)
140
25
<1
(min)
200
35
(%)
21.5
28.7
ND*

(BC)

Portland
( 3).
Klein

(C4A3 S ) ,
. BSFC1
25 10
. BSFC2

.
,

C4A3 S .
,
[5.15]

C 4 A3 S 2C S H 2 34 H
C 3 A.3C S .32 H 2 AH 3

C 4 A3 S 6Ca (OH ) 2 8C S H 2 74 H
3C 3 A.3C S .32 H

AH 3 3Ca (OH ) 2 3C S H 2 20 H
C 3 A.3C S .32 H

(5.6.1)
(5.6.2)
(5.6.3)

C: CaO, S : SO3, A: Al2O3, H: H2O

148

5.

Klein CaSO4/C4A3 S = 2.
BSFC1
4.5

C4A3 S CaSO4
[5.17],
.
BSFC2
1
Klein
(flash setting)
.
5.6.2. .

(MPa)
BC
BSFC1
BSFC2
1
17.6
14.9
2
5.0
25.8
23.5
7
17.5
36.8
30.1
28
53.7
43.7
34.2

,
, BSFC1 BSFC2
17.6 15MPa , 26Mpa
23.5MPa . , BC
2
5MPa. 7

Klein
(17.5MPa).
(36.8MPa BSFC1 30.1MPa
BSFC2). BC
,
149

5.

.
, C2S,

.
28 ,
53.7MPa
BSFC1 BSFC2 43.7MPa 34.2MPa .

150

5.

5.7
,

.
(Green
cements) (1250-1350oC)
(
CO2) Portland.

BC BSFC1 BSFC2
.
, (BC)
( 2 )

,
CaOSiO2-Al2O3-Fe2O3 CaO-SiO2-Al2O3-Fe2O3-SO3.
4CaO.3Al2O3.SO3
Klein .
Klein 2
(BSFC1 BSFC2),
28 ,

10
20MPa .

Portland EN
.3.3 3, ,
BC BSFC2 32.5N

151

5.

(2 ) (28 )
. BSFC1
42.5N OPC.
, ( , )

. ,
Portland
,
,
Klein
5.6.1-5.6.3.

152

5.

.5
Bogue

C-S-F-A .
4 , CaO, SiO2,
Fe2O3, Al2O3 1450C

4CaO.Al2O3.Fe2O3

(C4AF,

),

3CaO.Al2O3 (C3A, ), 3CaO.SiO2 (C3S,

) 2CaO.SiO2 (C2S, ).

Al2O3
CaO
Fe2O3
SiO2

102
56
160
60

Fe2O3 CaO Al2O3

Al2O3
CaO .

.
:
1.

Al 2 O3

MB Al2O3
MBFe2O3

Fe2O3

102
0.64(% Fe2 O3 )
160

153

5.

CaO

4 MBCaO 4 56

1.4(% Fe2 O3 ) ,
MBFe2O3
160

C4AF. Al2O3
CaO
. C4AF

%C4 AF 1.4(% Fe2O3 ) 0.64(% Fe2O3 ) (% Fe2O3 ) 3.043(% Fe2O3 )

2. Al 2 O3( ip ) (% Al 2 O3( ) ) 0.64 (% Fe 2 O3 )
CaO

3 MB CaO 3 56

1.65(% Al 2 O3( ) ) C3A

MB Al2O3
102

CaO. C3A

% C 3 A 1 . 65 (% Al 2 O 3 ( ) ) (% Al 2 O 3 ( ) )
1 . 65 [(% Al 2 O 3 ( ) 0 . 64 % Fe 2 O 3 )] [(% Al 2 O 3 ( ) ) 0 . 64 (% Fe 2 O 3 )]
2 . 650 (% Al 2 O 3 ) 1 . 692 (% Fe 2 O 3 )

3.

To

SiO2

CaO

2 MBCaO 2 56

1.87(% SiO2 ) , CaO

MBSiO2
60

,
C 2 S 1.87(% SiO2 ) (% SiO2 ) 2.87(% SiO2 ) . To CaO

C 2 S

2 MBCaO MBSiO2
MBCaO

2 56 60
3.07(%CaO )
56

C 3 S 3.07(%CaO ) (%CaO ) 4.07(%CaO ) .

4. C2S
3 CaO
C3S (= 3.07(%CaO ) ).
, C2S C3S

154

5.

%C3 S 4.07(%CaO() ) 4.07(%CaO() 1.4%Fe2 O3 1.65% Al2 O3() 1.87%SiO2 )

4 .07[% CaO ( ) 1 .4 % Fe 2 O 3 1 .65 (% Al 2 O 3 0 .64 % Fe 2 O 3 ) 1 .87 % SiO 2 )

4 . 07 (% CaO ) 1 . 43 (% Fe 2 O 3 ) 6 . 72 (% Al 2 O 3 ) 7 . 60 (% SiO 2 )

C 2 S 2.87(% SiO2 ) 3.07(%CaO( ) ) 2.87(% SiO2 ) 3.07

%C 3 S

4.07

2.87(% SiO2 ) 0.75(%C 3 S )

C-S-F-A

[5.18].

155

5.

B.5

C-S-F-A- S

C4AF, C4A3 S , C S C2S.

Al2O3
CaO
Fe2O3
SiO2
SO3

102
56
160
60
80

Bogue,
,
1. %C4AF =

4 56
102
(%Fe2O3) +
(%Fe2O3) + %Fe2O3
160
160

%C4AF = 3.0375%Fe2O3

2. %C4A3 S = (%Al2O3

102 C 4 AF
102 C 4 AF
80

) +
(%Al2O3
) +
160 3.0375
3 102
160 3.0375

4 56
102 C 4 AF
(%Al2O3
)

3 102
160 3.0375

%C4A3 S = 1.99(%Al2O3 -

102 C 4 AF

)
160 3.0375

156

5.

3. %C2S = %SiO2 +

2 56
(%SiO2)
60

%C2S = 2.87%SiO2

4. %C S

= 100 - 3.0375%Fe2O3 - 1.99(%Al2O3 -

102 C 4 AF

) 160 3.0375

2.87%SiO2

157

5.

.5
C-S-F-A 1350oC
C4AF,
C3A C2S Portland.

Al2O3
CaO
Fe2O3
SiO2

102
56
160
60

Bogue,
,
1. %C4AF =

4 56
102
(%Fe2O3) +
(%Fe2O3) + %Fe2O3
160
160

%C4AF = 3.0375%Fe2O3
2. %C3A = (%Al2O3

3 56
102 C 4 AF
102 C 4 AF

)+
(%Al2O3
)
160 3.0375
160 3.0375
102

%C3A = 2.647(%Al2O3 -

3. %C2S = %SiO2 +

102 C 4 AF

)
160 3.0375

2 56
(%SiO2)
60

%C2S = 2.87%SiO2

158

5.

.5

(5)

(6)

(7)

(
)
%.
11.71

(3)

0.00

2.320

18.700

0.100

0.180

49.200

18.030

Al2O3

7.93

11.59

CaO

36.69

53.63

54.18

100.00

45.810

11.400

53.000

24.730

3.620

1.590

SiO2

11.62

16.98

17.15

0.00

10.920

10.700

0.200

12.760

14.300

70.850

Fe2O3

5.17

7.55

7.63

0.00

2.200

43.000

0.070

0.040

23.000

3.700

TiO2

0.08

0.12

0.000

4.160

0.000

0.000

0.000

0.000

Na2O

0.16

0.23

0.120

3.730

0.000

0.000

0.000

0.410

K2O

0.42

0.62

0.600

0.060

0.050

0.000

0.000

1.720

MgO

1.63

2.38

1.900

0.190

1.300

1.850

0.000

0.570

SO3

6.32

9.23

0.000

0.000

0.000

39.300

0.230

0.000

31.60

0.00

37.210

9.040

44.200

23.140

13.890

10.510

%C2S

0.00

(4)
%

70.00%

2.00%

0.00%

16.00%

12.00%

0.00%

%C4AF

0.00
SiO2%

0.00

Fe2O3%

0.00

Al2O3%

0.00

(1)

9.33

0.00

%C S

0.00

%C4A3 S
%C3A

0.00

%C3S

0.00

CaO%

100.00

0.00

SO3%

0.00

0.00

(2)

159

5.

:
1. (1).
2.
-
(2).
3.
(3).
4.
(4).
5.
(5)
ignited base
(6).
6. (6)
(7). (7)
(3) ifend if .
7. (7)
0.5% (3),
.

160

5.

5.8
[5.1] Ernst Worrell, Lynn Price, C. Hendricks, L. Ozawa Meida, Annual
Review of Energy and Environment, Vol 26, 2001.
[5.2] C.D Lawrence, Production of Low-Energy cements, in: P.C
Hewlett, Leas Chemistry of Cement and Concrete, fourth ed., Elsevier
Butterworth-Heinemann, Oxford, 1998.
[5.3] J. Barrett, The roles of carbondioxide and water vapour in
warming and cooling the Earths troposphere, Spectrochimica Acta,
51A (1995) 415-417.
[5.4] P. Livesey, Alternative fuels for cement kilns, Society of Chemical
Industry, London lecture (1996).
[5.5] J.F Young, M.U Khan Afridi, Innovative Cements, in: J.I. Bhatty,
F.M.

Miller,

S.H.

Kosmatka,

Innovations

in

Portland

Cement

Manufacturing, first ed., Porland Cement Association, Skokie, Illinois,

USA, 2004.
[5.6] J. Stark, A. Mller, R. Schrader, K. Rmpler, Existence
conditions of hydraulically active belite cement, Zement-Kalk-Gips 34
(1981) 476-481.
[5.7] Ellis Gartner, Industrially interesting approaches to low-CO2
cements, Cement and Concrete Research 34 (2004) 1489-1498.
[5.8] Keith Quillin, Performance of belite-sulfoaluminate cements,
Cement and Concrete Research 31 (2001) 1341-1349.
[5.9] C.D Popescu, M. Muntean, J.H Sharp, Industrial trial production
of low energy belite cement, Cement and Concrete Research 25 (2003)
689-693.

161

5.

[5.10] J. Beretka, B. de Vito, L. Santoro, N. Sherman, G.L Valenti,

Hydraulic behaviour of calcium sulfoaluminate-based cements derived
from industrial process wastes, Cement and Concrete Research, 23
(1993) 1205-1214.
[5.11] M.M Ali, S. Gopal, S.K Handoo, Studies on the formation
kinetics of calcium sulfoaluminate, Cement and Concrete Research,
24 (1994) 715-720.
[5.12] S. Sahu, J. Majling, Phase compatibility in the system CaOSiO2-Al2O3-Fe2O3-SO3 referred to sulfoaluminate belite cement
clinker, Cement and Concrete Research, 23 (1993) 1331-1339.
[5.13] Liang Zhang, Muzhen Su, Yanmou Wang, Development of the
use of sulfo- and ferroaluminate cements in China, Advances in
Cement Research 1 (1999) 15-21.
[5.14] J.H Sharp, C.D Lawrence, R. Yang, Calcium sulfoaluminate
cements-low energy cements, special cements or what?, Advances in
Cement Research 11 (1999) 3-13.
[5.15] V. Kasselouri, P. Tsakiridis, Ch. Malami, B. Georgali, C.
Alexandridou, A study on the hydration products of a non-expansive
sulfoaluminate cement, Cement and Concrete Research, 25 (1995)
1726-1736.
[5.16]

M.

Katsioti,

P.E

Tsakiridis,

S.

Leonardou-Agatzini,

P.

Oustadakis, Examination of the jarosite-alunite precipitate addition in

the raw meal for the production of sulfoaluminate cement clinker,
Journal of Hazardous Materials, B131 (2006) 187-194.
[5.17] J.I. Bhatty, F.M. Miller, S.H. Kosmatka, Innovations in Portland
Cement Manufacturing, first ed., Porland Cement Association, Skokie,
Illinois, USA, 2004.

162

5.

[5.18] C.D Lawrence, The constitution and specification of Portland

cements, in: P.C Hewlett, Leas Chemistry of Cement and Concrete,
fourth ed., Elsevier Butterworth-Heinemann, Oxford, 1998.

163

6.

(Cr(VI))
.

.
pH
, (l:s ratio).


pH.
,
.
Langmuir, pH 5,
1 : 200:1.
pH pH 12-13
, .

, ,
.

6.1
,
2.27Gt/y [6.1].

(~1500C)

165

6.

.

. ,
,
+III +VI
. Cr(III)
,
. Cr(VI)

, ,
.
,
,

.
2003/53/EC

0,0002 %
[6.2].
.
,
,
()
.
(FeSO4.7H2O), , ,
, .. [6.3].


.

166

6.

1. hydrogensulphite:
4CrO3(s) + 6NaHSO3(aq) + 3H2SO4(aq) 2Cr2(SO4)3(aq) + 3Na2SO4(aq) + 6H2O

(6.1.1)

2. iron(II) sulphate:
2CrO3(s) + 6FeSO4 (aq) + 6H2SO4(aq) 3Fe2(SO4)3(aq) + Cr2(SO4)3(aq) + 6H2O

(6.1.2)

()
() .


(absorption) .


.
, ,
, ,

, , ,
, , [6.4,6.5].



.

.

(F-) [6.6], (3-) [6.7], (PO4-3)
[6.8-6.10],

(As) [6.4,6.11,6.12], (Cr) [6.13,6.14]

167

6.

(Zn), (Cd), (Cu),

(Pb) (Ni) [6.15-6.16].
,
,
. ,
.
.

[6.17].
Bayer
Na
Si Al (sodalite, sodium silicates .)
.

,
.

,
.


[6.17].

240C500C
( 6.1.1).
,
168

6.

.
2, 2.2.7
.

Al2O3.3H2O
Ca+Fe
Ca+Al

+OH-

Al2O3.H2O

CaCO3

6.1.1. .

.
.

pH ,
(l:s ratio).

169

6.

6.2

()
.

[6.6-6.8,6.11,6.13] 10g
190ml 12.6ml HCl 37%wt
20min.
Na
Si Al (sodalite, sodium silicates)
.

800ml pH
8 35ml (NH4OH),

Al(OH)2 Fe(OH)3
50C 10min.
,

500ml
.
110C 24 .
~500C 2h
(

-OH)

170

6.

6.2.1

, 6.2.1.1-6.2.1.3.

1400

1
5

1200

1000

Counts

800

600

1
400
200

4
3
2 7 2 2

0
10

4
6

5
4
2 8
3
2 4 3 3
7 81
7

7
4
42 8
7

20

1
1

30

40

4 1
35

50

60

70

2-Theta-Scale

6.2.1.1. XRD .

1400

1
5

1200
1000

Counts

800

600

1
400

200

1
6

7
8

1
1
3

33

0
10

20

30

40

50

60

70

2-Theta-Scale

6.2.1.2. XRD
HCl.
171

6.

1200

1
2

1000

Counts

800

600

1
1

400

200

0
10

20

30

40

50

60

70

2-Theta-Scale

6.2.1.3. XRD
500oC.

6.2.1.1.
6.2.1.1.
.
M
M

A/A

*
**
1

Fe2O3

Na6Ca2Al6Si6O24(CO3)2.2H2O

X
X
3

AlO(OH)

X
Calcium
Aluminum
4
Ca3AlFe(SiO4)(OH)8

X
X
Iron Silicate
Hydroxide
5

CaTiO3

Al(OH)3

X
Potassium
Aluminum
7
KAl3(CrO4)2(OH)6

X
X
Chromium Oxide
Hydroxide
8

CaCO3

X
X
* , **

172

6.

,

,

potassium aluminum chromium

oxide hydroxide ,

,
.

6.2.2

6.2.2.1,
[6.12,6.14].

10m2/g, 30m2/g (
) 64m2/g ( )
.
63m2/g,
70m2/g,
(130m2/g
155m2/g ).

,

.
CaO
(3.84%.)

TiO2

(8.50%.)

Na2O

(6.03%.) ( CaO 15.80%., TiO2 3.50%.

Na2O 3.80%.)
.

173

6.

6.2.2.1.
.

6.3

20ppm .
20g

()

2L

.

pH (t)
(l/s ratio = 100:1)
(T=25oC).
pH 4-12
1-5 .

174

6.

pH HCl
(Titrando

842 Device, Metrohm,

6.3.1) 20ml
.

6.3.1. , Titrando 842, Metrohm.

.
,

.
(

C Cr

CC r

C Cr

100%)

6.3.2.

175

6.

100

pH 5
pH 5
pH 6
pH 5

Cr(VI) (%)

90
80
70
60
30
20
10
0
0

(h)

6.3.2.
pH 4-12 : 100:1.

pH 5
6 .
pH 7-12 4
.
pH ,
. pH 5
25% 15%
. pH 6 10%
5% , pH 7 12
.
,
pH
( 6.3.3).

176

6.

Cr(VI) (%)

100

Cr(VI) 20ppm
t=1h

90

80

20

10

0
3

10

11

12

13

14

pH

6.3.3. Cr(VI) pH.

177

6.

6.4

/
.
10ppm
. 100 ml
0.1g ( s/l 1:1000), 0.2g
( s/l 1:500), 0.3g ( s/l 1:333), 0.4g ( s/l 1:250)
0.5g ( s/l 1:200) 1h.


/.
, 0.2g 100ml
10ppm, 20ppm, 40ppm 80ppm
.


.
pH 5
1
.
6.4.1 6.4.2
.
.

.
178

6.

Cr(VI) (%)

100

Cr(VI): 10 ppm
pH 5

80

60

40

20

0
0

(g/L)

6.4.1. Cr(VI)
.

Cr(VI) (%)

10

0.2 g /100ml
pH 5

5
0

10

20

30

40

50

60

70

80

90

100

Cr(VI) (ppm)

6.4.2. Cr(VI)
.

179

6.

[6.13].
,
,
Langmuir.
Langmuir

C
1
1

C
X Xm
bX m

( 6.4.1 ),

C
X ( g L-1) : Cr(VI) g .
C ( mg L-1) : Cr(VI) .
b ( L mg-1) :

X m ( mg g-1) : .
m b
,
6.4.1.


(
6.4.1), 6.4.3.

180

6.

6.4.1.
Langmuir.

mg Cr(VI)

(g/L)
100mL
Cr(VI) (ppm)
1
0.094
0.940
2
0.180
1.800
3
0.264
2.640
4
0.338
3.380
5
0.424
4.240

g /L Cr(VI)

5
4
3
2
1
0

10

Cr(VI) (ppm)

6.4.3. Langmuir Cr(VI)

25C pH 5.

Langmuir
0.999.

C
1.2218C 0.1766 (6.4.2),
X

Xm b Langmuir.
Cr(VI) (Xm) 0.82mg g-1
b -6.90 L mg-1.

181

6.

,
(0.5mg g-1) [6.18],

(1.6mg g-1 1.4-1.8mg g-1 ) [6.19,
6.13]
(145mg g-1 371mg g-1) [6.21, 6.22].

182

6.

6.5

Portland
,
Portland 1.7 3 ( 6.5.1)

. 10g
100ml 15 .

.

6.5.1.

%
SiO2
21.82
Al2O3
5.56
Fe2O3
4.12
CaO
67.37
MgO
1.07
1.16
K2O
Na2O
0.25

101.35

%
C3S
65
C2S
13
C3A
8
C4AF
13

3g

. ,
.

,
6.5.1.

183

6.

50

Cr

45

39,900

40
35

mg/L

30
25
20
15
10

5,200

5
0

6.5.1. Cr ,
.

,
.

.

,

.

() .
,

. 10g
100ml ,

6.5.2.

184

6.

0.20

Cr

0.18

0,154

0.16
0.14

mg/g

0.12
0.10
0.08
0.06
0.04
0.02

0,015

0,025

0.00

..

. & . .

6.5.2. Cr
.

,
0.15mg g , 10
.
,
,
.

.
6.5.3

4.7-4.8mg/L.

185

6.

10

Cr
8

mg/L

5,200

5,300

6.5.3. Cr ,
.

186

6.

6.6

.
Na Si Al

.
pH, pH
5 6 pH 5.


.
,
10m2/g 70m2/g.
pH 5, 25oC, 1
/ 100:1,
25%.
(~15%)
(~65%),
.
,

(160m2/g) .


.

,

187

6.

1000:1 200:1.
Langmuir 0.82mg Cr/g .

0.015mg/g 0.150mg/g.


.
pH

(pH 12-13),
pH (4-7) .

. ,

, pH
(pH 1213).

188

6.

6.7
[6.1] www.cembureau.be.
[6.2] Directive 2003/53/ec of the European Parliament and of the
Council of 18 June 2003.
[6.3] L. Hills, V.C Johansen, Hexavalent Chromium in Cement
Manufacturing: Literature review, Portland Cement Association, PCA
(2007) R&D Serial No. 2983.
[6.4] H.S Altundogan, S. Altundogan, F. Tumen, M. Bildik, Arsenic
adsorption from aqueous solutions by activated red mud, Waste
managment 22 (2002) 357-363.
[6.5] D. Mohan, C. U. Pittman Jr, Activated carbons and low cost
adsorbents for remediation of tri- and hexavalent chromium from
water, Journal of Hazardous Materials B137 (2006) 762811.
[6.6] Y. Cengeloglu, E. Kir, M. Ersoz, Removal of fluoride from aqueous
solution by using red mud, Separation and Purification Technology 28
(2002) 81-86.
[6.7] Y. Cengeloglu, A. Tor, M. Ersoz, G. Arslan, Removal of nitrate
from aqueous solution by using red mud, Separation and Purification
Technology (2006) doi: 10.1016/j.seppur.2006.02.020.
[6.8] J. Pradhan, J. Das, S. Das, R.S Thakur, Adsorption of phosphate
from aqueous solution using activated red mud, Journal of Colloid
and Interface science 204 (1998) 169-172.
[6.9] B. Koumanova, M. Drame, M. Popangelova, Phosphate removal
from aqueous solutions using red mud wasted in bauxite Bayers
process, Resources, Conservation and Reycling, 19 (1997) 11-20.

189

6.

[6.10] Y. Li, C. Liu, Z. Luan, X. Peng, C. Zhu, Z. Chen, Z. Zhang, J.

Fan, Z. Jia, Phosphate removal from aqueous solutions using raw and
activated red mud and fly ash, Journal of Hazardous Materials 137
(2006) 374383.
[6.11] H. Genc-Fuhrman, J.C Tjell, D. McConhie, Increasing the
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191

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