PCA R&D Serial No.

2556

Management of Detached Plumes in

Cement Plants
by F. MacGregor Miller
Presented at 2001 IEEE-IAS/PCA Cement Industry Technical Conference

Portland Cement Association 2001

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MANAGEMENT OF DETACHED PLUMES IN CEMENT PLANTS

By
F. MacGregor Miller
Construction Technology Laboratories, Inc.
Abstract
The paper examines the phenomenon of detached plumes in cement plants. A discussion of
reasons why such a plume forms is followed by a presentation of the various types of detached
plumes (steam plumes, organic plumes, sulfuric acid mist, ammonium salts, etc.) A discussion of
the chemistry occurring to cause these plumes is then offered, followed by a number of
remediative measures that may be effective in ameliorating these plumes, offered on a sitespecific basis. Emphasis is placed on the fact that to eliminate such plumes, one or more of the
contributing chemical species must be controlled.
Introduction
Detached plumes are a phenomenon in industrial processes, characterized by the observation
that no opacity is observed directly above the outlet of the stack, but that further downstream,
typically two to four stack diameters, a plume appears. The plume may be of various colors
white, blue, gray, and yellow or brown are the most commonand it may be of highly variable
density. The opacity associated with such a plume is not read by an in-stack opacity meter, since
within the stack there is normally little or no observable opacity. For this reason, detached
plumes are sometimes termed reactive or dynamic plumes, or pseudoparticulate plumes,
because most of the particulate matter responsible for their visibility is not present as particulate
in the stack, or in the inlet to the kiln dust collector. It is important to stipulate that if the opacity is
attributable to condensation of water droplets from steam only, there may be a detached plume,
but it will not be considered as such in this article. Such a detached plume will completely
evaporate further downwind, without any trail off; no emissions are actually occurring in such a
case.
Even detached plumes that show a trail off of pseudoparticulate matter are often more of a
visual nuisance than an actual pollution event. The actual amount of particulate matter that they
represent is usually rather small. Their visibility is usually due Nonetheless, their very visibility
makes them a potential problem for the manufacturer, because the neighbors can clearly see the
emissions, and are often concerned that they may constitute something harmful. For this reason,
although there are not yet any nationwide regulations governing the control and elimination of
detached plumes, they are assuming increasing prominence among issues that concern
manufacturing plants, particularly cement plants, in their dealings with local regulators.
Why does a Plume Form? Theory of Light Scattering
100% transmittance is a term implying the light from a source can be viewed without any
attenuation. By contrast, 100% absorbance or scattering would result in no light being detected.
Light passing through a plume is scattered by particles in the plume. The degree of light
scattering is determined by the path length, concentration of the particles, and physical properties
of the particles. These physical properties include the mean particle size, particle refractive
index, and particle density. Large particles will have a very small effect on opacity, while very
small particles will have a large effect. The largest effect will be for particles with diameters

comparable to the wavelength of visible light (about 0.4 to 0.7 m), as shown in Fig. 1
(Dittenhoefer, 1984).

Fig. 1Nominal Opacity Factor (light attenuation) vs. Particle Size

Examination of Fig. 1 shows that either large (>5 m) or small particles (<0.1 m) do not affect
opacity as much as particles with diameters in the range of the wavelength of visible light.
Assuming that the concentration of particulate matter remains constant, and that the path length
(related to the plume thickness) remain constant, it is reasonable to suppose that the opacity will
increase as the fraction of the particles in the size range of interest increases, normally either at
the expense of the finer particles, or because further particulate matter forms from gases in the
plume.
Types of Detached Plumes
The state of our knowledge of detached plumes does not permit us to identify all the chemical
species that may contribute to detached plumes; at present, however, there seem to be five
general categories of plumes that may develop during the process of clinker manufacture in
rotary cement kilns:
1.
2.
3.
4.
5.

Actual dust particulate

Condensation of semivolatile organic compounds
Formation of sulfuric acid mist
Condensation of ammonium salts (usually sulfates or chlorides)
Formation of water droplets with dissolved salts

Discussion of material that is actually present as particulate before reaching the stack is not part
of the scope of this paper. Let us deal with each of the other four plume types in order.
Organic Plumes
Combustion in cement rotary kilns occurs at very high temperatures (850-950C in calciners,
1550-2000C in kiln burning zones). In addition, residence times of fuels and oxidizers at high

temperature are long. For this reason, cement kiln emissions of organic species arising from fuel
are unusual. Most organic emissions arising from cement kilns are derived from the raw
materials (Hawks and Rose, 1995, Shkolnik and Miller, 1996). Many limestone deposits, and
also deposits of other raw materials, contain organic residues. The thermal treatment that these
raw materials undergo in the rotary kiln will have a major impact on whether any emissions occur.
If the organic material is very nonvolatile (like carbon, or soot, in many high carbon fly ashes), it
will tend to be burned in the calcining zone of the kiln. In such a case, it will probably contribute
to the fuel value, without creating emissions. Even in cases where the organic is incompletely
combusted, it may not create a plume. For example, it may be oxidized only to carbon monoxide.
CO forms no plume. Even if only vaporized, it may not create visible emissions; it is clear that the
organic material will have to condense in order to create opacity. Small molecules like methane
(CH4) and ethane (C2H6), which are gases at normal temperatures, are often created in the
pyrolysis of raw meal organic material. These cannot create a detached plume. Even volatile
liquids like benzene (C6H6) or methanol (CH3OH) will ordinarily not contribute to visible plume
formation. However, heavier semivolatile organics can and do contribute to such plumes. The
more volatile the organic impurity is, the more likely it is to vaporize without combustion (of
course, it is probably unnecessary to point out that if the organic were a gas at ambient
conditions, it would have already evaporated before reaching the raw mill).
Formation of Sulfuric Acid Mist
In high temperature combustion processes, including boilers and cement kilns, the vast majority
of any fuel sulfur is converted to sulfur dioxide. Sulfur trioxide is unstable with respect to
decomposition to sulfur dioxide at these temperatures (Bartlett, 1987; Greer, 1988, Miller and
Young, in press). The dependence is illustrated in Fig. 2, taken from the work of Bartlett for
smelters.

Fig. 2- Conversion of SO2 to SO3 for Various O2 Levels

Furthermore, because cement kilns are operated with limited amounts of excess air, and because
they contain large amounts of highly reactive lime and alkali for dry scrubbing of sulfur oxides, the
vast majority of sulfur oxides derived from fuels are captured within the kiln system and are not
emitted. The principal exceptions to this rule are when kilns are operated under reducing (fuelrich) conditions, or when there is a high circulating load of sulfate and kiln dust is not wasted to
relieve the cycle.

By contrast, the sulfur content of raw materials, if it is present in the form of pyritic or organic
sulfur, or elemental sulfur, can be emitted as sulfur dioxide because it is generated at low
temperatures (400-600C) where there is very little free CaO, and where the low temperature and
short residence time in the system preclude efficient capture by the kiln system. Even here,
however, although the temperature may be conducive to oxidation of the SO2 to SO3 (the reaction
is favorable at moderate temperatures), the reaction is slow, and the content of oxidant (free
oxygen) is low. Even where there is more oxygen, the dry scrubbing of the oxidized sulfur is
more efficient (Greer, 1988). As a result, there is usually not very much sulfur trioxide or sulfuric
acid emitted from cement kilns, particularly dry process kilns. On the other hand, where there is
water vapor present, oxidation of sulfur dioxide is much more favorable (Dittenhoefer, 1984).
Especially where ammonia is also present, or other catalytic species, the oxidation is favored
(Chadbourne, 1995, Chadbourne et al., 1980). This is attributed to the reaction of hydrogen
peroxide from the gas stream, in solution, with SO2, similar to the oxidation of SO2 occurring in
the impingers of EPA Method 6.
SO2 + H2O2

H2SO4

(The sulfuric acid is actually in the form of hydrogen and sulfate ions in solution). When the water
evaporates, the sulfuric acid remains. For these reasons, cement kilns processing raw materials
containing significant levels of pyrite raw material may observe a detached plume due to sulfuric
acid, even if ammonia is not present.
The opacity attributable to any given level of sulfuric acid mist is a function of the moisture
content of the gases. Mueller and Imhoff (1994) illustrate this situation in Fig. 3, where the line
represents equivalent opacity. It is clear that the opacity at 100% relative humidity occurs with
only 10% of the sulfuric acid mist needed at 40% relative humidity.

Fig. 3Equal Opacity Line for Sulfuric Acid Mist Concentration vs. Relative Humidity

Another factor important for the visibility of sulfuric acid mist plumes is the particle size
distribution, as observed in Fig. 1. Dittenhoefer (1984) provides an interesting insight into the
growth of aerosol particles in a plume as a function of time, as shown in Fig. 4. As plumes ripen,
they get higher concentrations of the particles whose size is in the range of visible light
wavelengths. Conversely, of course, the plume is dispersing. The relative rates of these
processes will dictate how visible the plume becomes.

Fig. 4Plume Particle Diameter Size Distribution vs. Time

These consideration help to explain why these sulfuric acid mist plumes, or indeed any detached
plumes, are more visibly prevalent in cool mornings, with high relative humidity, as opposed to
warm, dry afternoons.
Formation of Ammonium Sulfoxide and Ammonium Chloride Plumes
Although fuels contain nitrogen, this nitrogen is usually completely oxidized to nitrogen or oxides
of nitrogen in the combustion zones of cement kilns, and does not result in emissions of
ammonia. However, for the same reason that cement raw materials contain organic impurities,
they also contain organic nitrogen compounds. Proteins are the building blocks of life, and are
composed of amino acids, which are organic nitrogen compounds. It is reasonable to postulate
that when such compounds are heated, ammonia will be driven off, just as heating organic
carbon compounds breaks them down into simpler molecules like methane or ethane. Cheney
and Knapp (1987) showed that heating the shale from a plant experiencing a detached
ammonium chloride plume resulted in the generation of a significant amount of ammonia; Gray
and Ankenman (in press) have made similar observations.
Ammonia can be burned at high temperatures to nitrogen, or to nitric oxide:
2NH3 + 1 O2
4NH3 + 5O2

N2 + 3H2O
4NO + 6H2O

At lower temperatures, however, ammonia may escape oxidation. If the ammonia is driven from
the kiln feed at a low enough temperature, it may be emitted. Also, if the quantity is too high,
some may escape oxidation even if generated or introduced in the temperature range where
oxidation is favorable. Such a situation may arise, for example, if ammonia is deliberately
injected into the calcining zone to reduce NO emissions:

2NH3 + 3NO

2 N2 + 3H2O

This is the so-called SNCR (selective non-catalytic reduction) process for control of NOx
emissions.
If the ammonia has an opportunity to react with sulfur oxides generated from oxidation of kiln feed
pyrites, or if it encounters hydrogen chloride from chlorides introduced with fuel or kiln feed,
ammonium salts may form. In the case of the interaction with HCl, this will result in the formation
of ammonium chloride salt in the plume:
NH3 + HCl

NH4Cl

The ammonium chloride will normally not form inside the stack, because the temperature is too
high; Chadbourne (1995) and Hawks and Rose (1995) have established that the HCl and
ammonia are still unreacted until emitted from the stack. This is the reason that the opacity meter
does not react to the material. But the water droplets formed by condensation of water vapor
from the stack gases provide a medium for the reaction. Guemez-Garcia and Ganatra (1994)
give an example of this situation. Ammonia and HCl were derived from the limestone. The
ammonia was driven off between the second and third stages of the preheater. Chloride was
largely captured in the lower stages of the preheater, but some HCl was driven off, presumably by
reaction of chlorides with sulfur oxides and water vapor at high temperature. The preheater exit
temperature was 385C, high enough that the ammonia and HCl were not captured in stage 1 of
the preheater. HCl levels in the stack were 55-90 ppmv, while ammonia was about 27 ppmv.
The plume was highly visible. The plant solved the problem by increasing the number of
preheater stages, such that the preheater exhaust temperature was now down to 260C. At this
temperature, the chloride was effectively captured by the limestone. One of the two reactants
responsible for the plume (chloride) was reduced to less than 5 ppmv, and the plume
disappeared. This result was despite the increase in ammonia emissions, to 40-50 ppmv.
The situation with ammonium sulfoxide compounds is similar. Ammonium sulfates have higher
boiling points, so they may show some opacity in the stack. (Ammonium sulfate has a
dissociation temperature of 280C). The actual compounds formed may vary, depending on the
relative amounts of ammonia and sulfur oxides, and on which sulfur oxides are present:
NH3 + SO3 + H2O

NH4HSO4 (ammonium bisulfate)

2 NH3 + SO3 + H2O

(NH4)2SO4 (ammonium sulfate)

NH3 + SO2 + H2O

NH4HSO3 (ammonium bisulfite)

Other compounds can be formed, such as ammonium sulfite, or ammonium sulfamate

(NH4SO3NH3) (Chadbourne, 1995; Chadbourne et al., 1980). Any of them can result in a
detached plume. We referred earlier to ammonium sulfoxides, rather than ammonium sulfates,
because of the plurality of compounds possible. In the authors observation, these ammonium
sulfoxide plumes are the most common of all cement plant detached plumes, since so many raw
materials contain pyrite impurities and organic nitrogen compounds. Such a plume was the
subject of work by Dellinger et al. (1980). The authors determined the actual chemistry of the
plume, and found 4.5-ppmv ammonium sulfate, 200-ppmv sulfur dioxide, 170-ppmv ammonia,
and water. The plume is only visible when the conditions are cool and moist; when the sun rises
high in the sky and the temperature increases, the water cannot condense until the plume is
dispersed, and very little opacity results.

The problem with ammonium salts and detached plumes is especially prevalent for plants
operating with in-line raw mills. The raw mill often operates at temperatures around 150-200C.
At this temperature, the ammonium salts may condense. They go back into the kiln feed, back
into the kiln system, where they vaporize again. They subsequently condense again in the raw
mill (unless a small amount of the ammonia is burned or decomposed). When the raw mill is
taken off line, the volatile salts are no longer captured in the raw mill, and go to the dust collector.
Since the dust collector cannot capture the new, high concentrations efficiently, the plume
becomes highly visible. When the raw mill is put back into operation, the plume ceases again.
This cycle continues indefinitely, unless something is done to break it.
Studying Plumes at Cement Plants
One of the problems in evaluating detached plumes at plants is sampling. It is difficult to get
samples of the actual species responsible for the plumes by stack sampling. EPA Method 5 is a
good method for determining actual particulate matter, but the condensable salts will be found in
the probe, on the filter, or in the impingers, depending upon which salts are present and at what
temperatures the collecting devices are maintained. Methods that involve impinger collection of
stack gases will bring virtually all potential plume reactions to completion, so that concentrations
of ammonium salts, for example, will be overestimated (MacIver et al, 1988, Chadbourne et al.,
1980). It is really necessary to sample the actual plume to determine concentrations. This was
actually done at several cement plants (Hawks and Rose, 1995; Dellinger et al., 1980; Cheney
and Knapp, 1987, Mueller and Imhoff, 1994). This is an arduous and expensive process, but
unavoidable to obtain realistic data.
Plume Remediation
Now we finally get around to the title of this presentationManagement of Detached Plumes in
Cement Plants. We need to determine what measures to adopt to get rid of the detached plume.
To do so, we first must determine which of these plume types is applicable. For example, if the
plume is attributable to organic compounds, we need to determine the source of the organic
compound. Let us examine a few possibilities:
1. The organics are due to poor combustion in the calciner. Testing reveals that the calciner
exhaust has 60 ppmv of total hydrocarbons. Maybe the fuel and air are not properly mixed in
the calciner. Perhaps the oxygen or CO analyzers at the calciner exhaust are not working
properly. Fixing these problems may solve the plume problem.
2. The organics are due to oil in the mill scale used for an iron source in the raw mix. This is
established by running organic testing on each raw material. The mill scale is replaced with
an alternate iron source, and the problem goes away.
3. The organics are due to the limestone. Maybe the quarrying plan can be changed.
Otherwise, it may be difficult to solve the problem. In Colorado, two plants changed their
pyroprocessing systems and installed one-stage calciner kilns. These kilns took the raw
materials immediately up to 850Cat this temperature, organics are immediately
combusted and are therefore not emitted.
Let us examine another casea plant has a persistent detached plume that is attributable to
ammonium sulfate. To get rid of the ammonium sulfate, we need to get rid of one of the two
reactants that ultimately form ammonium sulfateeither the ammonia or the SO2. The use of
hydrated lime to react with SO2 has been used successfully to remediate some plumes (Schwab
et al., 1999; Hawks, Schwab and Stuehmer, 1999; Hawks and Rose, 1995; Wolf and Seaba,
1994). The hydrated lime is introduced into the downcomer, or into the kiln feed, or into the dust
collector, in the form of slurry, or a dry powder. In the case of Inland Cement (Hawks, Schwab,
and Stuehmer), the use of very fine lime, with a high specific surface area, was successful in
remediating the plume. Because of the low temperature region in which the lime is introduced,
the reaction rate is slow, and needs to be enhanced with reactive lime. When the lime is
introduced in the form of slurry, the additional water also helps the reaction.

Perhaps the optimum solution involves getting rid of the source of ammonia. Certain industrial
byproducts may contain precursors of ammonia. Aluminum dross, as an example, often contains
aluminum nitride that may generate ammonia when contacted with water or steam. If aluminum
dross is used as an aluminum source, it may be responsible for the generation of ammonia. It is
important to remember that at least one of the gases (either ammonia or sulfur oxides) must be
treated if the plume is to be removed.
Guemez-Garcia and Ganatra (1994) provide another type of solution to the plume problem. In
this case, as earlier noted, the issue was ammonium chloride. A reduction in temperature,
achieved by introducing an additional preheater stage, brought about capture of the chlorine in
the systemchlorine which had earlier escaped the preheater. Again, one of the two reactants,
the HCl, is removed from the exit gases (even though the ammonia concentration actually
increased!). Of course, the plant needed to install air cannons to deal with the higher circulating
load of chloride that resulted.
Another possible plume problem is sulfuric acid mist. Here, the literature provides worthwhile
input as to remediation. The excess oxygen concentration will affect the SO2/SO3 balance. The
more SO2 and less SO3 in the plume, the less likelihood of a detached mist plume. Of course, the
moisture level will also play a role, whether in the plume itself or in the atmosphere. Wolf and
Seaba (1994) provide another solution for the acid mistthey recommend hydrated lime
injection. As with the sulfur component of the ammonium sulfoxide plume, the hydrated lime will
reduce the SO2, SO3, and/or H2SO4 concentration, and thereby remediate the plume.
Finally, we can cite certain measures that may be efficacious on a case-by-case basis. It will be
noted that dispersion of the plume, before condensation of its components can occur, has been
cited as a reason why the plume disappears when the day warms up and the relative humidity
decreases. Another way of causing the plume to disperse more rapidly is to increase its velocity.
This may or may not be practical on a particular site. The same argument can be applied to
heating the flue gases after the dust collector; they will disperse further before the dew point of
the gases is reached. On the other hand, if the flue gas temperature entering the dust collector
can be reduced, it may capture certain particulates that would otherwise pass through the dust
collector in the gaseous state. This solution may be particularly applicable to ammonium
sulfoxide plumes.

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