Glass Recycling in Cement Production An
Glass Recycling in Cement Production An
www.elsevier.com/locate/wasman
Abstract
An innovative approach of using waste glass in cement production was proposed and tested in a laboratory and cement pro-
duction plant. The laboratory characterization of 32 types of glass show that the chemical composition of glass does not vary sig-
nificantly with its color or origin but depends on its application. The alkali content of glass, a major concern for cement production
varies from 0 to 22%. For the glass bottles mainly found in Hong Kong waste glasses, the alkali content (Na2O) ranges from 10 to
19% with an average around 15%. There is no significant change of the SO2 content in the gas exhaust of the rotary kiln when
about 1.8 t/h of glass bottles were loaded along with the 280–290 t/h raw materials. The content of NOx, mainly depends on the
temperature of the kiln, does not show significant change either. The SO3 content of the clinker is comparable with that obtained
without the loading of glass. The alkaline content shows a slight increase but still within three times the standard deviation obtained
from the statistical data of the past year. The detailed analysis of the quality of the cement product shows that there is not any
significant impact of glass for the feeding rate tested. # 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Alkali; Nitrogen oxides; Rotary kiln; Solid waste; Sulfur oxides
Table 1
Chemical composition of some typical commercial glasses
Glassa
1 2 3 4 5 6 7 8 9 10 11
SiO2 80.5 73.0 77.9 71 73.5 61.5 72.68 63.0 72.0 57.3 75.3 68.0
Na2O 3.8 – 4.1 14 17 8.8 13.25 7.6 11.0 1.9 5.7 22.0
K2O 0.4 4.5 2.3 0 1.5 5.3 – 6.0 – 0.5 0.8 –
PbO – 6.0 – – 23.6 – 21.0 – – – –
Al2O3 2.2 – 0.8 – – – – 5.0 3.2 6.2 3.0
B2O3 12.9 16.5 14.1 – – – – 12.0 23.6 7.6 –
CaO – – 0.8 5 6 – 12.76 0.3 – 4.7 1.1 7.0
MgO – – – 3.5 4.5 – 0.26 0.2 – 8.7 – –
Fe2O3 – – – 0.01 0.8 – – – – – 3.0
MnO – – – – – – 0.2 – – – –
Others – – – – – – As2O3 – – BaO –
0.05 3.5
a
1, Pyrex 7740; 2, Pyrex 7720 (Nonex); 3, Silex; 4, modern lime bulb glass; 5, lead glass; 6, flat drawn window glass (Libby-Owens, American); 7,
American lead bottle glass; 8, borosilicate thermometer glass; 9, Jena Supermax (German); 10, Jena Gerate (German); 11, Christmas tree ornament glass.
Therefore the company can afford to increase its alkali 5. The dried samples were ground into fine powders
content by 0.2 wt.% which means over 3200 t of alkali, with a mortar and pestle followed by a screening
calculated based on an annual cement production of 1.6 using a sieve tower with an aperture of 250 mm.
million t. Secondly, an equilibrium between alkali and 6. The fine powder was finally transferred into
sulphur trioxide inside kiln atmosphere has to be main- labeled test tubes and sealed with plastic caps. It
tained to attain a stable operation. Before implementing was ready for analysis.
this innovative idea, there are two issues that have to be
addressed: the alkali contents in the waste glass and the The chemical composition of different types of glasses
quality of the cement produced. Hence a research team were analyzed using the surface-scanning technique of
was formed between Hong Kong University of Science X-ray photoelectron spectroscopy (XPS). In XPS,
and Technology and GIC first to carry out the char- monochromatic X-ray beams are concentrated onto the
acterisation of the typical waste glasses generated in sample surface where the inner K or L shell electrons
Hong Kong and then to conduct the plant trial. This are excited. By locating the peaks of energies in the XPS
paper reports the results obtained. spectrum, the existence and atomic percentage of a
respective element are deduced (Skoog, 1985).
Before starting to analyze the chemical components of
2. Glass characterisation various glasses, the results obtained using the XPS
method are compared with the data shown in Table 1.
The waste glass characterization was carried out in The good comparison of the literature data and those
the following procedures: obtained by the XPS method are given in Table 2. The
slight variations are possibly associated with different
1. Different types of glasses were collected and sources of glass.
labeled with descriptions including the materi- After verifying the analytical technique, various glas-
als contained, names and industrial codes (if ses were analyzed with the description shown in Table 3.
any). As it shows that the majority of glasses used in Hong
2. All contents of the bottles were disposed of or Kong is from the packaging, more samples were taken
stored in other containers. Then the bottles were from this category. Since color usually was taken as a
cleaned with detergent and DI water. primary parameter for the reprocessing of glass, its
3. For bottles with narrow openings, the mouths of relation with the composition is analyzed along with the
the bottles were cut off by a diamond saw. For glass application and origin.
other types of glass and bottles, pieces of glass The chemical composition of all the glasses analyzed
were obtained by hitting the totally wrapped is listed in Table 4. For packaging glasses, their alkali
glass with a hammer. contents are high (around 10% or higher) and the var-
4. The glass samples were washed again together iation is quite small (8–14%). The sodium oxide con-
with the mortar and pestle, and dried in an oven tents range from 10 to 19 wt.%. The average alkali
at 100 C for about 20 min. oxide content is found to be 15%, with a standard
G. Chen et al. / Waste Management 22 (2002) 747–753 749
Table 2
Comparison between literature data and analyzed results
Category Source O (%) Si (%) Na (%) K (%) Al (%) B (%) Ca (%) Mg (%)
Pyrex Literature 53.3 40.3 3.2 0.0 0.7 2.6 0.0 0.0
XPS 50.0 36.3 3.7 0.3 1.0 2.0 0.0 0.0
Light Literature 45.8 32.7 12.1 1.2 0.0 0.0 5.1 3.0
Bulb XPS 40.0 30.5 12.0 0.0 1.0 0.0 2.5 1.0
Window Literature 45.3 32.0 9.3 0.0 0.3 0.0 12.9 0.2
Glass XPS 41.0 30.0 12.0 0.0 1.0 0.0 3.0 2.0
Table 3
Description of the glass samples analyzed
deviation of 2%. Since packaging glass is expected to be usually Pyrex Borosilicate, the alkali metals had been
the majority of the recycled glass, the numbers obtained extracted out during their manufacturing. Although the
here can serve as good reference values for loading glass recycled from laboratory glass is more attractive to
design in the cement production. the cement production, the treatment of such glass is
The glass used in the domestic light bulb or tubes currently well established as chemical waste.
resemble those for packaging glass in terms of alkali Out of the 32 samples tested, nine different colors
contents, while the glass for microwave containers and were observed. Statistically, there is not a significant
computer monitors show distinctively low alkali con- difference found for the chemical compositions between
tents with sodium content being 5 and 7 wt.%, respec- transparent and colored glasses although color is an
tively. Insulation fibre shows the least sodium content, 1 important factor in the reprocessing of glass. Such a
wt.%. Laboratory glass also has low alkali content, 3 finding is not surprising because the coloring of glass
wt.%, which is expected because for these glasses, only requires a minute amount of metal oxides and
750 G. Chen et al. / Waste Management 22 (2002) 747–753
Table 4
Chemical composition of glass samples, by weight percent (%)
Sample no. O Si Na C Ca Al Mg K B F Cl Sr Zr Ba
1 Packaging 40 31 11 14 3 1 0 0 0 0 0
2 49 34 8 7 0 1 1 1 0 0 0
3 39 29 10 13 6 1 1 0 0 0 0
4 41 30 12 10 4 1 0 0 0 0 0
5 43 32 12 8 3 1 1 0 0 0 0
6 41 31 11 8 3 2 1 1 0 0 0
7 40 31 11 12 5 1 0 0 0 0 0
8 42 30 14 8 5 1 0 0 0 0 0
9 39 29 12 12 4 1 2 0 0 0 0
10 43 32 10 10 3 1 1 0 0 0 0
11 44 33 10 10 3 1 0 0 0 0 0
12 50 33 9 6 0 1 0 1 0 0 0
13 42 33 10 11 2 1 0 0 0 0 0
14 43 30 13 8 5 1 0 0 0 0 0
15 43 31 13 7 5 1 0 0 0 0 0
16 44 33 11 7 4 1 0 0 0 0 0
17 44 32 13 6 4 1 0 0 0 0 0
18 43 31 13 7 5 1 0 0 0 0 0
19 40 30 13 9 5 1 1 1 0 0 0
20 40 32 10 13 3 1 0 0 0 0 0
21 42 32 11 10 2 1 1 0 0 0 0
22 44 34 10 8 3 1 0 0 0 0 0
23 Domestic 40 30 13 12 3 1 0 0 0 0 0
24 40 30 13 12 2 1 2 0 0 0 0
25 42 29 15 7 3 2 2 0 0 0 0
26 40 31 11 14 3 1 0 0 0 0 0
27 52 36 5 6 0 1 0 0 0 0 0
28 39 28 7 9 1 1 0 5 0 0 0 4 1 4
29 Industrial 41 20 1 23 9 5 0 0 0 0 0
30 41 30 12 12 3 1 2 0 0 0 0
31 Laboratory 49 37 3 5 0 1 0 1 3 0 0
32 49 36 3 6 0 1 0 0 3 0 0
these metals are not alkali but nickel, cobalt, copper or Table 5
even iron. Besides the color, the origin of the glass does Sodium oxide content in different glasses (%)
not show any significant difference in the chemical Insulating fiber glass 1.5
composition, either. Laboratory test tube 4
Since in the cement industry the alkali content means Microwave glass plate 6.5
the alkali oxide content, it is more proper to convert the TV, computer monitor 9.5
Coca Cola bottles 12
alkali into alkali oxide. It should be noted that the
Wine bottles 12–17.5
number of moles of oxygen in glass is insufficient to Sauce bottles 12–17.5
convert all metals and silicon to their respective oxides. Soft-drink bottles 12–19
Some of these elements have to exist in their elemental Light bulbs 15
forms. We assume that all of the alkali content exists in Light tubes 20
its oxide form, i.e. Na2O and K2O. The average content
of sodium oxide is about 15 wt.% while that of potas-
sium oxide is still less than 1 wt.%. In cement terminol- 3. Comparison of class composition with cement
ogy, sodium oxide equivalent (Na2O)e or total alkali
content is often used, where (Na2O)e is equal to A detailed comparison between compositions of glass
0.658%K2O+%Na2O (Hewlett, 1998). Thus it is safe and Portland cement is given in Table 6. The glass
to say here that (Na2O)e is equivalent to average sodium composition is the averaged value of the data shown in
oxide content since the K2O is comparatively very low. Table 4 and the compositions of Portland Cement is
The sodium oxide contents of typical glasses are sum- from the American Standard of Test and Methods
marized in Table 5. It is remarkable to know that the (Annual Book of ASTM Standards). A simple compar-
sodium oxide content of the bottles found in Hong ison of the glass composition and that of Portland cement
Kong is significantly higher than that reported for the shows a significant difference. Beside alkali oxides, glass
American lead bottles as listed in Table 1 of class 7. contains approximately 67 wt.% of silica (SiO2) and
G. Chen et al. / Waste Management 22 (2002) 747–753 751
Table 6
Comparison of components of glass and Portland cement
Fig. 1 shows the flow chart of the cement production 4.2. Parameters analyzed
line employed by GIC. Bottles were fed into the mixing
chamber and fell down a distance of approximately 15 Two locations were selected to monitor the environ-
m to crush on the kiln orifice area. The temperature in mental impact, one at the gas exhaust before the elec-
the kiln orifice area was about 1100 C. The crushed trostatic precipitator (EP) and the other in the stack.
752 G. Chen et al. / Waste Management 22 (2002) 747–753
Table 7
The analytical results of the gas samples before EP
29 January 2000 29 January 2000 31 January 2000 31 January 2000 1 February 2000
a.m. p.m. a.m. p.m. p.m.
SO2 level was of key interest at the first location while mean before the trial started. Although the data pre-
NOx, SO2, O2 and OPAC levels were all important at sented in Tables 7–9 are for the first test, similar results
the second location. The SO3 and alkali content of kiln were obtained for the second test.
feed, third-stage material, fourth-stage material, EP The averaged sodium oxide content of all materials
dust and clinker were analyzed at an hourly interval were larger than the historical mean but the potassium
during the glass burning period. Comparison was made oxide content remains unchanged. Consequently, the
on chemical and physical parameters of cement with equivalent (Na2O)e or the total alkali content increased
and without waste glass feedings. noticeably (Table 10). The total alkali content of all
materials during glass burning period, however, was
4.3. Results and discussion also within 3 S.D. obtained from the data of 30 days
randomly chosen from the past year. It is useful to note
The monitoring stations show that there is no sig- that an increase in the sulphur supply is required in
nificant change in the NOx, SO2 and OPAC levels dur- order for the smooth operation of the kiln system.
ing the glass addition in comparison with the results No material built up due to increased alkaline content
obtained at normal working conditions as shown in could be developed or observed. Kiln operation and
Tables 7 and 8. The mean values in Table 8 were process control were normal during and after the trial
obtained from hourly emission monitoring for 21 h. The burn. No obvious change was found on clinker appear-
slight increase of SO2 content over that before the trial ance. The physical and chemical properties of cement
is probably due to the high sulphur content fuels used in using clinkers produced before glass feeding and during
order to balance the expected increase of alkali content. glass feeding were tested and shown in Table 11. The
This also explains why after the trial the SO2 content is difference between the values of alkali in Tables 10 and
even higher. However, the concentrations of the pollu- 11 resulted from the addition of fillers in the manu-
tants are well below the emission standards. facturing of cement. Table 11 clearly shows that there is
As for the processing material analysis, Table 9 shows no difference between the cement produced with and
that the SO3 of all materials during glass burning period without glass feeding both chemically and physically.
were within 3 times the standard deviation (S.D.)
obtained from the data of 29 days randomly chosen
Table 9
from the previous 7 months before the trial. The mean
The sulphur content in the burned material (% SO3)
values during the trial are averaged from the values
obtained every 6 h. They are comparable to those of the Before burning glass During burning
Table 10
The total alkali content in the burned material (%)
Mean S.D. Max Min Mean S.D. Max Min Mean S.D. Max Mm
Na2O KF 0.10 0.03 0.19 0.05 0.13 0.03 0.19 0.11 0.08 0.01 0.10 0.06
3rd-AVG 0.11 0.03 0.17 0.08 0.15 0.05 0.25 0.12 0.11 0.01 0.13 0.09
4th-AVG 0.16 0.03 0.22 0.12 0.20 0.03 0.25 0.18 0.17 0.02 0.21 0.15
EP 0.08 0.03 0.17 0.04 0.13 0.05 0.22 0.07 0.08 0.01 0.09 0.07
CLK 0.14 0.04 0.25 0.07 0.23 0.02 0.26 0.20 0.24 0.06 0.35 0.18
K2O KF 0.28 0.06 0.45 0.18 0.27 0.02 0.29 0.23 0.24 0.02 0.27 0.21
3rd-AVG 0.75 0.16 0.24 0.50 0.86 0.21 1.20 0.64 0.76 0.08 0.89 0.65
4th-AVG 1.14 0.21 1.67 0.86 1.25 0.14 1.46 1.08 1.14 0.13 1.34 0.92
EP 0.28 0.06 0.42 0.19 0.28 0.07 0.38 0.21 0.31 0.03 0.37 0.27
CLK 0.38 0.06 0.54 0.28 0.31 0.03 0.35 0.28 0.34 0.04 0.42 0.28
(Na2O)e KF 0.28 0.07 0.42 0.20 0.31 0.04 0.37 0.26 0.23 0.02 0.28 0.20
3rd-AVG 0.61 0.12 0.96 0.44 0.72 0.15 0.91 0.55 0.60 0.05 0.68 0.52
4th-AVG 0.92 0.15 1.27 0.71 1.03 0.11 1.17 0.88 0.92 0.09 1.05 0.78
EP 0.27 0.06 0.45 0.19 0.32 0.06 0.38 0.24 0.28 0.02 0.33 0.27
CLK 0.39 0.06 0.53 0.29 0.44 0.03 0.46 0.39 0.46 0.07 0.58 0.37
References
5. Conclusion
Environmental Protection Department (EPD) 2002. Waste. Hong
Thirty-two types of glass typically found in Hong Kong SAR Government. Available: http://www.info.gov.hk/epd/.
Glass Packaging Institute (GPI) 2000. Recycling. Available: http://
Kong were analyzed in terms of their elemental compo- www.gpi.org/.
sition. The composition of the glass does not relate with Wheeler, E.L., 1958. Glass and Its Working Characteristics. Inter-
its color, nor its origin. It depends on the glass applica- science Publishers, New York.
tion. The results are consistent with reported values Mebta, P.K., 1978. Cement Standards—Evolution and Trends.
American Society for Testing & Materials, Philadelphia, USA.
except that the sodium oxide content of the glass bot-
Skoog, D.A., 1985. Principles of Instrumental Analysis, third ed.
tles, 12–19%, is significantly higher than that reported Saunders College Publishing, USA.
for the American lead bottle glass, 7.6%. The general Hewlett, P.C., 1998. Lea’s Chemistry of Cement and Concrete, fourth
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