Journal of the Air Pollution Control Association

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The Composition of Glass Furnace Emissions

John D. Stockham

To cite this article: John D. Stockham (1971) The Composition of Glass Furnace
Emissions, Journal of the Air Pollution Control Association, 21:11, 713-715, DOI:
10.1080/00022470.1971.10469588

To link to this article: https://doi.org/10.1080/00022470.1971.10469588

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 The concentrations of participate matter, sulfur oxides, nitrogen oxides, fluorine
chlorine, and carbon monoxide in the emissions from two glass melting furnaces
were determined. Solids loadings averaged 2.1 and 5.4 Ib/hr or 0.029 and
0.041 grains/scfm of exhaust gas for the flint and amber glass emissions, re-
spectively. Sulfur trioxide averaged 17 and 15 ppm, by volume, while the
sulfur dioxide concentrations averaged 250 and 315 ppm. Fluorine and chlorine
concentrations were about 2 and 4 ppm, respectively. Nitrogen oxides con-
centration averaged 340 and 640 ppm. Carbon monoxide content in the flint
glass effluent was 375 ppm and in the amber glass effluent, 40 ppm. Particle
size and composition of the particulate matter in the emissions from the two furnaces
were determined using the electron microscope, emission spectrograph, and X-ray
diffractometer. The geometric median particle diameter, based on a size-fre-
quency distribution by number, was 0.11 ju for the amber glass emission and 0.13
H for the flint glass emission. Three forms of sodium sulfate were identified;
other elements identified as being present in major proportions were calcium,
magnesium, silicon, barium, and chromium.

The Composition of Glass Furnace Emissions

John D. Stockham
I IT Research Institute

The composition of the effluent dis-
charged to the atmosphere from two
side-port, regenerative, gas-fired, glass
melting furnaces is reported. One
furnace melted flint or clear glass; the
other melted amber or brown glass.
The grain loading of particulate matter
was determined by filtering a sample of
the effluent and weighing the material
collected. The morphological charac-
teristics and chemical composition of the
particulate matter were determined
using microscopy and spectroscopy
techniques. The gaseous contaminants
in the effluent were determined either by
adsorption on silica gel impregnations or
by scrubbing the gases in liquid im-
pingers. The effluents were tested for the
presence of the following gases, sulfur
trioxide, sulfur dioxide, nitrogen oxides,
fluorine, chlorine, and carbon monoxide.
The volume of effluent discharged was
determined from velocity data obtained
by a pitot tube traverse across a stack
diameter.
The major ingredients of soda-lime
glass are silica sand (SiO2), limestone
(CaO, MgO), soda ash (Na2CO3), and
cullet (broken glass). Minor ingre-
dients include salt cake (Na2SO4), niter
(NaN03), Feldspar (A12O3), arsenic,
(As) barium oxide (BaO), and boron
oxide (B2O3). Glass is colored by the
addition of minute amounts of the
oxides of nickel, iron, manganese, cop-
per, and cobalt, and elemental sulfur.
In the case of amber glass, carbon and a
sulfide or a sulfate are added.
Regenerative furnaces consist of a
dual chamber filled with brick checker-
work. While the products of com-
bustion from the melter pass through
and heat one chamber, combustion air
is preheated in the other chamber. The
function of each chamber is inter-
changed by reversing theflowof air and
combustion products. Reversals occur
every 15 to 20 minutes as required for
maximum conservation of heat. Screw
or reciprocating-type feeders contin-
uously supply batch blended material to
the furnaces. The dry material floats
upon the surface of the molten glass until
it melts. Carbonates decompose releas-
ing carbon dioxide. Particles entrained
in the gas bubbles and other volatilized
components of the feed stock are swept
from the furnace by the hot gases pass-
ing across the molten surface. These
materials are either deposited in the
checkers and refractory-lined passages
or discharged into the atmosphere.
Stacks are normally natural draft.
Furnace sizes, feed composition, and
processing techniques are considered
proprietary by the glass industry and
information of the furnaces tested was
not divulged during the study.
No air pollution control equipment
was in use. Rather, air pollution was
controlled by judicious ingredient selec-
tion and good operating practices.
Sampling Apparatus and Analytical
Methods
Gas volumes and velocities in the two
effluent stacks were determined by a
pitot-tube traverse across one stack
diameter. An "S" type pitot tube was
used.
The sampling train used to collect the
particulate and gaseous pollutants is
shown in Figure 1. It consisted of five
major elements, a probe, a filter, four
parallel impinger trains each with three
impingers in series, a dry gas meter, and
a vacuum pump. The probe was a
Vycor glass tube encased in an alumi-
num sheath. The probe inlet was one-
inch in diameter. A V/2 in. diameter
Teflon filter (Mitex LS, 90 mm, 5 ju pore

November 1971 Volume 21, No. 11 713

 -Vycor probe - 1 " aluminum Heat Table I. Flue conditions from the manu-
12 mm sheath facture of glass.
Flint Amber
Teflon coated filter holder glass glass
I I for particulate matter •Oven furnace furnace
I Heated pyrex glass manifold Flue diameter, f t 5 6
Inlet \Heat Average gas velocity,
28 mm Impingers- ^ ft/sec 16 33
Vycor
Average gas
Icebath-^ 1^01007 temperature, °F 619 1143
Static pressure,
in. H2O -0.44 -0.98
Impinger Absorbing solution Gas volume, scfm 8250 16800
1 80% isopropanol for SO3
2 Dil. H 2 0 2 for S0 2
3,6,9,12 Demisters
4,5 0.1 N NaOH for gaseous fluoride
7,8 Dil. H 2 0 2 for NOX
10,11 0.1 N NaOH for gaseous chtoride

Figure 1. Sampling apparatus.

Table II. Emissions from the manufacture

size, Millipore Filter Corp., Bedford, manifold leading to the impingers was of glass.
Mass.) was used to collect the partic- typically within the range of 250-295°F. Flint Amber
ulate matter. The Teflon filter was Carbon monoxide was estimated Emissions glass glass
selected because of its excellent chemical colorimetrically by adsorption on silica furnace furnace
resistance and temperature stability. gel impregnated with a complex silico- Solids, gr/scf 0.029 0.041
Normally, a glass fiber filter is chosen molybdate compound and a palladium Solids, Ib/hr 2.1 5.4
for filtering hot gases, but such filters sulfate catalyst (Mine Safety Ap- Sulfur trioxide,
would be inappropriate where the chem- pliance Co., Pittsburgh, Pa.). The ppma 17 15
Sulfur dioxide,
ical composition of glass furnace ef- effluent sample was withdrawn directly ppm 250 315
fluent was to be investigated. Ceramic from the stack through an air-cooled Fluorine, ppm 2.2 1.9
thimbles were considered too coarse to copper coil. The length of the coil was Chlorine, ppm 4.9 4.1
retain the ultra-fine particles antici- selected so that the gas temperature at Nitrogen oxides,
ppm 340 640
pated as the result of a presurvey in- the point of sampling was within the Carbon monoxide,
spection. range specified by the manufacturer ppm 375 40
After filtration the gas flow was split for the adsorber. ppm by volume for all gaseous pollutants.
equally among four parallel impinger The particulate matter collected on
trains. Each train consisted of three the Teflon filter was weighed and sub-
500-ml Greenburg-Smith impinger bot- mitted for elemental analysis by emis-
tles placed in series; the first two bottles sion spectroscopy and X-ray diffraction.
contained absorbing solutions; the third Special samples of particulate matter
was operated dry. Separate impinger for particle size analysis were collected
trains were used to collect the sulfur on electron microscope screens coated
oxides, the nitrogen oxides,fluorine,and with a thin film of carbon. Several
chlorine. During sampling the im- screens were attached to the Teflon
pingers were immersed in ice water. filter and, after preheating the filter and Table III. Spectrochemical analysis of
glass furnace effluent particulate matter.
The total volume of the sample was probe, a sample was withdrawn for a
measured by a dry gas meter. A brief period of time, 2-5 mins. These Estimated concentration of
samples were also used for compositional Element"
vacuum pump provided the source of
suction to withdraw the sample. Sam- analysis of individual particles by non- Flint glass Amber glass
ples were withdrawn at a fixed volu- dispersive X-ray. Elementb effluent effluent
metric sampling rate, about 3^ to 3^ Sulfur oxides were determined by a Silver Questionable Questionable
the stack velocity. Under these con- modification of the Seidman method.2 Aluminum Moderate Weak
ditions the samples would over-estimate Fluoride interference was eliminated by Boron Questionable Questionable
the proportion of large particles. How- Barium Not detected Strong
substituting strontium chloride for bar- Calcium Very strong Very strong
ever, errors due to anisokinetic sam- ium chloride and the excess strontium Chromium Moderate Strong
pling of particles below 5 /* are neg- ion was back titrated with diso- Copper Moderate Weak
ligible.1 dium-ethylene-dinitrilotetraacetic acid Iron Moderate Moderate
Magnesium Strong Moderate
The probe, filter, and manifold were (EDTA) using Eriochrome Black T as Manganese Moderate Very weak
preheated prior to sampling. Once an end-point indicator. Sodium Very strong Very strong
sampling was begun with the amber Inorganic chloride and fluoride were Lead Very weak Weak
glass effluent, only intermittent aux- absorbed in 0.1 N sodium hydroxide Silicon Strong Moderate
Tin Not detected Very weak
iliary heating was needed to maintain solutions. Chloride was determined Strontium Questionable Moderate
the probe and filter in the temperature with a chloride specific electrode (Orion Titanium Trace Trace
range of 350-400°F. Because of the Research, Inc., Cambridge, Mass.). Vanadium Trace Weak
lower gas temperature of the flint glass Potassium nitrate, 2M, was added as Zinc Weak Weak
effluent, thefilteringtemperature ranged an ionic strength adjuster. Fluoride a
Very strong, 10—100%
from 270 to 300°F. The temperatures was determined colorimetrically using Strong, 1—10%
Moderate, 0.1—1%
were selected so that filtration was ac- Amadac-F, a lanthanum-alizarin che- Weak, 0.01—0.1%
complished above the dew point of sul- late. Dorsey and Kemnitz3 showed Very weak, 10—100 ppm
Trace, 1—10 ppm
fur trioxide. The temperature of the that this method compared favorably b
Elements not listed were not detected.

714 Journal of the Air Pollution Control Association

with other fluoride analytical pro-
cedures. They also reported that a
glass probe serves as a reactor to con-
vert volatile fluorides into silicon tetra-
fluoride. Nitrogen oxides were ab-
sorbed in aqueous hydrogen peroxide.
Because halides interfere with ASTM
method D 1608-60 using phenoldisul-
fonic acid, the method proposed by
Johnson4 was used.
Results and Discussion
The stack gas velocities and volumes
for the amber glass and flint glass efflu-
ents are given in. Table I. The solids
loading and gaseous composition of the
effluents are reported in Table II. The
results reported are the average of two
30 min samples. One reversal of the
gasflowin the furnaces occurred during
each sample collection period. The
flint glass furnace was operating at
100% design capacity during sampling
while the amber glass furnace was
operating at 90%. The solids con-
centration in the two effluents were
0.029 and 0.041 gr/scf but, because of
the difference in gas volumes, the amber
glass furnace discharged more than
twice the solids per hour. Chlorine,
fluorine, sulfur oxides, nitrogen oxides,
and carbon monoxide were found in
both stack gases. Chlorine, fluorine,
and sulfur trioxide concentrations were
similar in the two effluents.
A spectrochemical analysis of parti-
cles collected on the filters, Table III,
showed the elements present in major
proportions in flint glass effluent were
sodium, calcium, magnesium, and sili-
con. The major elements in the amber
glass effluent were sodium, barium,
chromium, and calcium. An elemental
analysis was also made by non-disper-
sive X-ray. Sulfur, chromium, iron,
nickel, calcium, aluminum, copper,
zinc, silicon, and magnesium were re-
ported. Sodium is beyond the detec-
tion limit of non-dispersive X-ray
analysis. Also, sulfur is unreported
0.6
0.5
0.4
0.3
I 0.2
Flint glass- \
0.1
•c 0.05 p\
£ 0.04
0.03
0.02
0.05 0.2 12 5 10 20 30 50 70 80 90 95 98 99
Percent by number equal to or less than indicated size
Figure 2. Log-probability distribution of particle sizes present in
glass furnace effluent.
November 1971 Volume 21, No. 11
by d.c. graphite arc emission spec-
troscopy because of its non-metallic
nature. Arsenic was not found by
either method. However, arsenic pro-
duces very low level line intensities and
in small amounts is difficult to detect.
Three forms of sodium sulfate were
identified by X-ray diffraction. These
were sodium sulfate (1), sodium sulfate
(III), and thenardite. Thenardite is
the orthorhombic crystal form; Form
III has a tetragonal crystalline struc-
ture. Sodium sulfate (III) and pos-
sibly Form (I) were identified in the
particulate matter collected from the
amber glass effluent. Thenardite was
excluded because the strong (Mines at
4.63 and 1.86 were absent. Some X-
ray diffraction patterns showed a dis-
continuity in several lines. This dis-
continuity indicates an absence of com-
plete randomness in the crystal orienta-
tion and suggests a slow cooling process
during crystallization.
The particles collected from the
flint glass effluent exhibited diffraction
patterns similar to thenardite and, pos-
sibly, calcium sulfate. The patterns
resembled sodium sulfate (III) except
the strong d-line at 3.73 was missing.
It was on the basis of the missing line
that the pattern was determined to be
thenardite rather than Form (III).
Calcium sulfate could be made to fit
quite a few of the extra lines in the
patterns.
The distribution of particle sizes in the
effluents was determined from electron
photomicrographs. The size-number
frequency data fitted the log-prob-
ability distribution function, Figure 2.
The geometric median particle diameter
of the flint glass particles was 0.13 ju
and the geometric standard deviation
was 1.5. Corresponding values for
the amber glass furnace effluent parti-
cles were 0.11 ju and 1.7, respectively.
Because of the low density (<5%
coverage) of the deposit, it is reasonable
to assume that the size distributions
_ gaseous fluorides," J. Air Poll. Control
>
Si
>
nC y
•-
-Amber glass.
99.8
represent the most prevalent particle
sizes in the effluents.
Conclusions
The results represent a study of the
effluents from two glass melting fur-
naces, one melting flint glass and the
other melting amber glass. The con-
centrations of particulate matter, sul-
fur oxides, nitrogen oxides, fluorine,
chlorine, and carbon monoxide in the
emissions were determined. Solids con-
centration in the flint glass furnace
effluent was 0.029 grains/scfm and in
the amber furnace effluent 0.041 grains/
scfm. Sulfur trioxide averaged 17 and
15 ppm for the two furnace effluents,
respectively. Sulfur dioxide concen-
trations averaged 250 and 315 ppm and
nitrogen oxides concentrations averaged
340 and 640 ppm. Fluorine and chlo-
rine concentrations were similar in both
effluents averaging about 2 and 4 ppm,
respectively. The carbon monoxide
content in the flint glass effluent was
375 ppm and in the amber glass ef-
fluent 40 ppm. The geometric median
particle diameter, based on a size-
frequency distribution by number was
0.11 /* for the amber glass and 0.13 n
for the flint glass effluent. Three
forms of sodium sulfate were identified
in the solid matter collected; other
major elements present included cal-
cium, magnesium, silicon, barium, and
chromium.
Despite the fact that the furnaces
tested are standard throughout the
glass industry, the emission levels re-
ported may not be representative of
other furnaces. Restraint is suggested
to avoid applying the results generally
to other furnaces. Testing of the ef-
fluents from more furnaces is recom-
mended in order to develop emissions
factors useful for predicting the pollu-
tion potential of glass melting furnaces.
References
1. Watson, J., "Errors due to anisokinetic
sampling of aerosols," Amer. Ind. Hyg.
Assoc. Quart., 15, 21 (1954).
2. Seidman, E., "Determination of sulfur
oxides in stack gases," Anal. Chem., 30,
1680 (1958).
3. Dorsey, J. and Kemnitz, D., "A source
sampling technique for particulate and
Assoc. 18,12 (1968).
4. Johnson, C , "Analysis of gas mixture
containing oxides of nitrogen," Anal.
Chem., 24,1572 (1952).
Mr. Stockham is Manager, Fine
Particles Research at IIT Research
Institute, Chicago, 111. This paper
was presented as Paper No. 70-72
at the 63rd Annual Meeting of the
Air Pollution Control Association
in June 1970.
715