47

STACK EMISSIONS

Return To T.O.C

T M LOWES
 STACK EMISSIONS

CONTENTS

1. INTRODUCTION

2. NOX

2.1 NOX Formation

2.2 NOX Reduction
2.3 Emission and Legislative Levels

3. SO*

3.1 SOZ Emission

3.2 Assessment of S02 Emission
3.3 S02 Emission Minimisation

4. HEAVY METALS

4.1 Heavy Metal Emissions

4.2 Environmental Impact

5. DIOXINS AND FURANS

5.1 The Concern

5.2 Dioxins. What are They?
5.3 Dioxins. How are They Formed?
5.4 Potential BCI lXoxin Problem Areas

6. Conclusion
1. INTRODUCTION

The emissions from the stacks of cement kilns until recently have mainly been entered around the
emission level of dust.

Technology now exists for any works to meet 50mg/Nm3, as is required in the UK by 1998.
However in the upgrading that takes place for a works to meet the 50 mg/Nm3 limit, 30 mg/Nm3
is a reasonable target for an average operating level.

It can be foreseen however that al O mg/Nm3 will be forthcoming in the Europe in the next
century.

This increa.sd environmental awareness has manifested itself into other areas of stack emissions,
for which limits have been set or are about to be set.

The list will obviously expand as more knowledge of the short and long term health impact of
various emissions are firther researched and debated.

It is the aim of this paper to deal with the species that are the currently most probable for
legislation in BCI in the next few years.

The typical emissions and probable legislative levels will be identifed and what can be done to
reduce these emissions and the impact of the reduction on the process will be discussed.

The species to be dealt with in this paper are NOX, SOZ, Heavy Metals (HM) and Dioxins and
Furans.

It is anticipated that the paper will have to be updated on a triemial basis due to the rapidly
changing state of emissions regulation in the UK and USA.
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To control the emissions ofNOx it is first necceassary to understand how it is formed. It has been
covered in the Flames lecture but is worthwhile repeating here for completeness.

Much has been written about NOXformation and destruction. Their formation is associated with
the Flame.

2.1 NOX Formation

It has been often claimed that emissions from power station are all fiel NO, and emissions from
cement kilns are all thermal NOX Neither of these statements are correct. As fw as the cement kiln
is concerned there is an underlying fiel NO, and a thermal NOXwhich is a finction of burning
zone temperature.

The principal reactions for thermal NO formation are:-

N2+0 + NO+N E =75 kcals/mole (1)

N+02 4 NC)+() E = 6 kcals/mole (2)

H+OZ + OH+O E = 16.5 kcal.dmole (3)

02 + 20 E =59 kcals/mole (4)

The formation of thermal NO is post flame front and is dictated by the temperature and oxygen
concentration.

The maximum formation rate of NO is with around 10% excess air for the combustion of the
volatiles. In these circumstances the oxygen atoms for reaction (1) are provided from the
oxidation of hydrogen/hydrocarbons via reaction (3) and super equilibrium O and OH
concentrations (x 100) occur.

If there is insufficient oxygen mixed into the flame to combust the volatiles near to stoichiometnc
then the oxygen atoms will be provided later in the kiln via the higher activation energy reaction
(4), less NO will therefore be formed.

Reaction (1) and (3) combine to give an overall activation energy of 91.5 kcals/mole. This in
effect means that no thermal NO is formed below 1600”C and the amount produced for the same
burner mixing conditions is very dependent on clinker combinability temperature and free lime.

Fig 1 shows a typical relationship between kiln back end NO levels and free lime as a fimction of
combinability temperature.

Fuel NO forms, from the nitrogen in the fiel. It is formed at a lower temperature than thermal
NO and is controlled by the availability of oxygen during the combustion of the volatiles which
contain the majority of the nitrogen.

3
A simple schematic reaction scheme is:-

IqNc+() + NH+co (5)

NH +02 + NO+ OH (6)

Clearly limiting the formation of oxygen atoms will reduce the formation of NO from both the fiel
(5) and thermal NO (1) routes.

Reducing burning zone temperature will also reduce the NO formed via the thermal route.

For burners with a high primary air, a maximum conversion of the volatile fhel nitrogen into NO
is possible as there could be enough oxygen available to combust the volatiles near to
stoichlometric without a significant amount of mixing. ,,

NO reduction by burner modifications can obviously be achieved, particularity in large diameter

kilns. Devolatilisation into a minimum of primary air appears to be the key to reduce the formation
of both fbel and thermal NO. The skill being to avoid reducing conditions in the process via an
optimum burner design and operation.

The CEMFLAME trials clearly identified the impact of early mixing and devolatilisation on NOX
emissions. Fig 2 shows a scatter diagram of the impact on the amount of air mixed into the coal
jet prior to devolatilisation on NOX. Fig 3 shows a linear regression applied to the same data.

The scatter at any particular mixing ratio is due to local micro mixing between the air and coal
channels. The reason that high volatile coals gave the lower NOX is that the volatiles came off
faster and a shorter ignition distance was possible.

The potential for low NOX burners via the lower primary air route is clearly identified, but only
if the ignition distance is not increased.

2.2 NOX Reduction

Techniques for the reduction of NOx emission fall readily out of a knowledge of their formation
kinetics.

Namely increased flame temperature increases NOX and reduced oxygen availability on
devolatilisation decreases NOX.

Hence NOX emissions can be reduced by:

● Lower burning zone temperature, ie higher free lime, lower LSF, lower combinability
temperature;
● Lower flame temperature, ie flue dust injection, water addition, liquid recycled fbels,
higher excess air;
● Flame front nearer the burner, ie bluff body, finer grind, higher volatile coal;
● Lower primary air, ie indirect firing;
● Optimum distribution of primary air, ie customised multichannel burner.

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● Staged combustio~ ie modi&ing precalciner design to ensure that the coal volatiles
combust sub stoichiometric, via two stage combustion principles that are applied in boiler
NOX reduction technologies.

All these possibilities have potential consequences on the flame and process performance. Multi-
channel burners specifically designed for low very NOX, have been reported (Dykerhoff, CBR)
to being extremely detrimental to kiln output and plant performance.

The above techniques describe flame measures, other possibilities exist based on destroying the
NOX after it is formed.

These generally involve reactions in a specific temperature window= 1000”C, with either NHg
or hydrocarbon radicals (CH).

The use of NH~ to reduce NOX emissions has been demonstrated in gas risers in Germany. It is
effective, but costly and can have an NH~ emission downside. Reductions of 20/30°/0 have been
achieved.

The use of CH radicals to reduce NOX emissions has been demonstrated by the use of tyre chips
in the scoops at Westbury and into the gas riser to the pre-calciner at Cauldon. In addition tyres
and tyre chips injected into the Aalborg kiln via a FLS cannon have significantly reduced the NOX.

Reduction of 20/30V0 again appear possible. A sub stoichiometric condition has to exist for the
NOX reduction reaction to take place.

A simple reaction mechanism being:

2N0 + CH + NZ+CO+OH (7)

2.3 Emissions/Legislative Levels

As NOX is used a major control parameter for LINKman, while it is normally referred to as NOX,
it is in reality NO in ppm at the kiln back end at 1- 4°/0 oxygen.

N02 is normally a maximum of 50ppm.

Typical average back end NO levels range from 800 to 2000 ppm. The higher levels being
associated with hard burning, due to either combination problems or operator preference.

Typical legislative limits that are being considered in the UK are 1200-1600 mg/Nm3 of NOX
calculated as N02 at the stack, at “the oxygen level at the stack.

To convert NO in ppm to NOZ in mg/Nm3 it is necessary to multiply by (14+32)/22.4 = 2.05.

Typical dilution factors at the stack from the back end is around 2.

While most BCC works can meet the 1998 levels some are begiming to have problems from the
results of their plume modelling and the perceived result of their NOX emissions on the
background levels.

Europe has generally lower levels set than is currently being proposed in the UK, mean levels of
800 mg/Nm3 are being proposed, with regulation concerning the peak levels and their frequency.
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3.1 ~ Emission

The S02 emissions from cement kilns arise principally from the S in the raw materials, however
they are supplemented via the S in the fiel.

Kilns with Iron Pyrites (FeS) in the raw material loose at least 50’?40of the Sup the stack. This is
due to the fhct that the FeS burns in the preheater (dry process shale), before a significant amount
of CaO has been produced to capture the S02. Some SOZ is captured in the conditioning tower
and some in the raw mill, however significant emissions occur.

Dunbar and to a lesser extent Hope works have this problem. Emissions at Dunbar can be in the
range 2-3000 ppm SOZ.

Generally if there is no FeS in the raw meal and the total SOS input is in stoichiometric ratio with
the alkahs, afier an allowance for C12is made, there is very little chance of a significant S02
emission in any process providing the “Flame is good”.

Typically for a kiln with an N~O equivalent of 0.6% a total SOS input of 0.77?40on clinker gives
a molar ratio of 1, in the absence of Clz.

A 0.05’%0C12on clinker reduces the SOS input on clinker for an effective molar ratio of 1 to
0.71?40.

Above a molar ratio of 1, the S forms CaSO~ and K2SOd.2CaSOd. Both these compounds are not
as stable as the alkali suiphates. CaSO~ in particular breaks down read~ly with reducing conditions.

Avoiding reducing conditions is a must for any wetisemi wet kiln to meet SOZ emission
regulations. While for a dry process reducing conditions do not necessarily increase SOZ
emissions, considerable process problems occur due to sulphate deposits at the kiln back end, in
the gas riser and in the cyclones.

Fig 4 shows the impact of reducing conditions created via lowering the back end oxygen, on the
S02 emission from a semi wet process. Normal operation was at 2% oxygen with around 50 ppm
of S02, decreasing the oxygen level to the range 1.0-1. 5°/0, produced S02 emissions up to
800ppm. This effect was for a clinker with alkalis of 0.6?40N~O equivalent with the ?40SOqat the
molal equivalent.

A similar situation has been found in dry process kilns where the increased S02 manifests itself
into preheater blockages.

CaSOJ is stable thermodynamically up to around 1450”C in the presence of oxygen. Even above
this temperature it’s dissociation is kinetically controlled. If 2000ppm of CO is in contact with the
CaSO1 at temperatures above 1000”C, it will begin to be reduced to CaO and SOS, resulting in
severely increased SOS concentrations in stage IV.

It should be noted that CO levels of 2000ppm can be the result of poor burner design and
operation as well as low back end oxygen.

9
 TABLE 1

CALCULATED S02 EMISSIONS

In~uts : 100t~h, 800 kcaldkg, no dust durn~ed, RMF 1.55

Raw Meal ~ Retention Clinker S02 Emission

?foso3 Yos %’ ‘/0s03 mg/N m3

0.3 1.5 90 0.79 290

0.3 1.5 95 0.84 145

0.3 3 90 1.16 430

0.3 3 95 1.23 215

0.3 4.5 90 1:52 565

0.3 4.5 95 1.61 280

0.5 4.5 90 1.74 640

0.5 4.5 95 i.83 320

Corwersion factor for ppm S02 from mg/Nm3 os 80/22.4= 3.6

3.2 Assessment of SO, Emission

The assessment of the emission levels of SOZ is not an easy matter.

Contracting for external agencies to measure the emission can result in very low levels if they
have no experience in cement kiln emission measurements. The presence of fine dust can adsorb
the S02 as it is cooled.

Cross duct measurement although accepted in Germany, can read incorrectly due to the fact that
their is not a discrete spectral window and a range of cross correlations need to be made.

A mass balance on the cement kiln S input is a viable alternative.

A programme is available to calculate the emissions which incorporates, fiel and raw meal inputs
as well as dust dumping.

Care has to be taken in the dry process to ensure that the raw meal SOS is the true figure and not
what is fed to the kiln.

Table 1 gives some typical calculations.

Some high retention factors are required to meet forthcoming UK regulation of 750 mg/Nm3,
which equates to only 210 ppm.

While this carI readily be met by a dry process without FeS in the raw meal, wet processes using
high levels of pet coke will have difficulties. Fortunately all BCC wethemi-wet kilns have dust
scoops which make the retention somewhat easier.

3.3 SO, Emission Minimisation

As outlined in section 3,1 the emissions of S02 area finction of the:-

● Type of S in the raw meal, FeS being a potential problem are%

● Total S input to the system;

● Process type, with the wet process having the highest potential for S02 emissions;

● Oxygen level in the kiln, reducing conditions must be avoided;

● Hard burning if the SOS to alkali molar ratio is greater than 1.

The only reahstic solution to high levels of FeS in the raw meal, if a significant reduction in SO*
is required is flue gas desulphurisation.

The main control to minimise SOZ emission apart from limiting the S input is kiln oxygen.

Masons operate at 60/70% pet coke with SOZ emission levels according to Procal, well below
750mg/Nm3. This has been achieved by experimentation to identi@ the kiln back end oxygen level
at which a sudden increase in S02 emission takes place. LINKman is then set to control above this
level.
 TABLE 2

HEAVY METALS - LIMITS - EMISSIONS

Name Ml!’@?! IPR 5/1 Limits Weardale Emissions* Weardale RawMeal*

mg/N m3 mglNm3 PP m

GrouD 1 metals

Mercury Hg 0.1 I <0.0001 0.03

(%ouD 2 Metals

Thallium T1 Total Group 2 0.0006 0.3

Cadmium Cd 01 00003 0.7

&ouD 3 Metals

Antimony Sb <00001 1.55

Arsenic As 0.0001 6

Chromium Cr 0.0009 21

Cobalt co Total Group 3 <0.0001 7.4

Copper Cu 1 0.0006 10

Lead Pb 0.14 405

Manganese Mn 00045 945

Nickel N1 0.0021 33

Tin Sn <0.0001 0.9

Vanadium v 0.0093 29

*Measurements druing a test 7/12/94

4. HEAVY METALS

4.1 Heaw Metal Emissions

The words Havy Metal @l) conjure up a range of images, mainly fear from the uninformed.

The French used to call them trace elements, which is more nearer the realistic situation as regards
the Cement Industry.

Table 2 lists the current HM’s and their emission limits for Hazardous Waste Incinerators in the
UK.

An EU Hazardous Waste Incineration Directive is due for implementation before the end of
decade, which effectively cuts the emission limits of IPR 5/1 by 50%.

Despite all the claims that cement kilns are not designed to meet Hazardous Waste Regulations,
the HM emissions measured at Weardale at well below even the forthcoming EU Directive.

One of the reasons for this is that the Weardale precipitators operate at an average of around
20mg/Nm3. While HM emissions are not pro-rata to dust emissions, it could be expected that the
HM emissions would be around 2.5 times higher at an emission level of 100mg/Nm3.

However it should be noted that the Pb levels in the Wearda.le raw meal are exceptionally him
due to the local geology, a more normal range being 20-100ppm.

Emissions mainly result from the loss of raw meal, concentrated by the more volatile metals.

Figure 5 gives tiorrnation on the temperature required for the metals to have a vapour pressure
of 1mm, ie O.13°/0 of this metal in the vapour phase. This clearly indicates that the majority of
elements condense above 10OO°C.

This has proven to be the case from a detailed analysis of the Weardale raw meal and CKD.

5O-1OOVO of the Hg Tl, Cd and Pb concentrates on the CKD. The remaining HM’s are of a similar
level to the raw meal.

Assuming the most consmative case in that all of the emissions referred to in table 2 result from
the raw meal, with no inputs from the fiel apart from the Vanadium, capture efficiencies are
calculated and shown in Flg 6 using the same programme as was used to assess the S02 emissions.

In can be seen that the lowest capture efficiency is Hg at 99.4%. This completely explodes the
myth that Hg in is Hg out.

Weardale precipitators operate at around 100”C. Precipitators that operate around 250°C, could
be expected to loose around 20V0 of the Hg due to it’s volatility.

Generally above 99.9V0 of the Class 3 metals are retained in the Weardale system.

13
 Fig 5

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 Heavy Metals Kiln Capture Efficiency
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100

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Heavy Metal
Weardale “Coal” Firing, 850 Kcals/kg 13% 02 dry,
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4.2 Environmental Imr)act

One could assume that if the emissions of HM’s were below the forthcoming EU Hazardous
Waste Directive then the Environmental Impact would be acceptable.

While this is true burning conventiomd fbels, the use of the words “Recycled Liquid Fuels (RLF)”
has become synomonous with cries of Toxic Wastes, Deadly Emissions, etc.

Generally in RLF the maximum levels of HM’s is around 3000 ppm. This compares with levels
in petcoke of 1500- 10,000ppm.

At an RLF replacement rate for coal of 40%, the equivalent of 405 ,ppm of Pb in the raw meal is
12000ppm in the RLF. The maximum anticipated Pb in the RLF is 1000ppm, < 10% of the total
Pb input tr~L,,{
~‘I wte~ potentially increasing the Pb emission by 0.001 mg/Nm3 if the same capture
efficiency iS :” ;!: .ained. Evidence is available that indicates that the capture efficiency increases
with total HM input. Hence the increased emissions will be even lower than predicted.

Environmental Impact assessments are normally carried out with’ referencp to the Maximum
Exposed Individual(MEI). This is the person who happens to live their life in the position of
maximum plume concentration.

The relationship between that emitted from the stack and that seen by the MEI is evaluated by
plume modelling, based on the meteorological data, stack height and local topography.

Dilution factors of between 105 and 106 are the norm.

This is the compared to the either the Environmental Quality Standards(EQS) if they are available
or the Environmental Assessment Level(EAL), in the absence of EQS’s.

The EQS for the MEI for Pb is 2p/Nm3.

Typical dilution factor to the MEI for the O.14mg/Nm3 emission of Pb identified in table 2 results
in an average concentration to the MEI of between 0.001 # and 0.000 14@m3.

This gives a ration of Process Contribution(PC) to EQS of 0.07 to 0.007’?40.

In the more recent drafi guidance notes from HMIP releases are considered to be insignificant if
PC/EQS is< 0.2%.

In addition there is cause for concern if PC/EQS is ~2?40.

Hence there should be no concern over these emission levels. Indeed Pb emission levels up to
around 0.3 5mg/Nm3 should not be the cause on any concern, for the most conservative case of
dilution factor.

This ties in quite neatly with the forthcoming EU Hazardous Waste Incineration Directive.

Hence HM emissions do not have a significant environmental impact, whether or not RLF is
being used.

16
5. DIOXINS AND FURANS

5.1 The Concern

IfHM’s produce public concern with particular reference to RLF, they are small beer compared
to the very thought of dioxin and furans.

HMIP were fairly relaxed about RLF trials in cement kilns until the draft EPA report on dioxins’
emission levels ranked cement kilns as the third highest emitter of dioxins in the USA and
effectively reduced the World Health Organisations tolerable level of dioxins from
10pgTEQ/kgbwt/day as a tolerable level, to O.OlpgTEQ/kgbwt/day for a 1 in 106 risk of catching
cancer.

This produced two problems, firstly cement kilns are high emitters of dioxins and secondly they
are very toxic.

The i.niiormation in the EPA report also indicated that kilns burning wastes produced at least 10
times higher dioxin emissions than normal fhels.

Average emission levels of above 10ng/Nm3 TEQ were being quoted for Hazardous Waste kilns
and around 0.9ng/Nm3 TEQ for fossil fiel fired kilns.

While the data quoted were real, they were at fault in two areas:

● the data was old and taken before cement operators knew the impact of ESP temperature
on dioxin emission;

● the emissions from some of the Hazardous Waste using kilns were taken under worst case
scenarios as dictated by EPA situations that would not exist in practise.

As the UK Hazardous Waste Incinerator regulations IPR 5/1 speci~ and maximum dioxin
emission of 1nglNm3, the EPA data obviously produced a considerable amount of public concern.

It also caused considerable consternation in the UK, where no measurement above lng/Nm3, had
been measured in any kiln, which also corresponded to European data.

5.2 Dioxins. What are Thev?

Dioxin is a generic name to cover all forms of dioxins and iirans.

There are comprised of two benzene rings comected by either one or two oxygen molecules with
up to eight chlorine atoms. Dioxins have two oxygen atoms, firans one.

There are 210 forms, all of which have different levels of toxicity.

They are normally reported as the equivalent of their most toxic form, ie the 2378 TEQ equivalent
in ng/m3.

17
Table 3 lists the typical dloxins that are normally measured. Only 17 of the 210 cogeners are toxic.
The second column gives the relative toxicity factor. This ranges from for the 2378 tetra-dioxin
to 0.001 for the Octa dioxin and iiu-an,

Table 3 represents the maximum emission that has been measured from Weardale works. This was
without any RLF being used and is 0.074 ng/Nm3 TEQ, with a total Tetra-Octa emission level of
8.33nglNm3.

As stated previously emission limits for Hazardous Waste incinerators is currently 1 ng/Nm3.

EPA are currently considering setting a 30 mg/Nm3 emission level for Tetra-Octa emissions.

Municipal incinerators, coal and wood fires have at least an order of magnitude higher emissions.

5.3 Dioxins. How are they Formed?

Reaction Engineering International of Salt Lake City, who can call on the services of most
eminent Academics at MIT,etc, have been recently investigated the emissions of D&F’s in cement
kilns. The following comments are based on the work and an extensive knowledge of combustion.

Two major pathways have been identified for the formation of dioxins, namely

● Post flame homogeneous gas phase formation;

● Catalytic heterogeneous formation from organic precursors similar in stfucture to

dioxins, either on particles in flight, or on particles captured in the electrostatic
precipitators.

The temperatures that exist in cement kilns mean that any hydrocarbon no matter how complex
or chlorinated will be completely combusted in the flame, provided there is suficient oxygen.

The combustion rate being at least 500 times faster than in the afterburner of the most modem
incinerator.
,,
It should also be noted that the coal molecule is more difficult to combust completely than any
chlorinated organic. In addition coal on a total chlorine input basis can have as much C12as an
RLF on a 40?40replacement with 1.5% chlorine. UK coals with up to 0.6% Clz exist.

In addition tests carried out in several installations indicate very high (>99.9997%) destruction
and removal efficiencies (DRE) for chlorinated organics and SF6. Where the DRE found was
controlled by the detection limit of 1ug/m3.

Consequently there will be no unreacted chlorinated hydrocarbon matter to be converted to

dioxins in the optimum temperature for gas phase formation (880-980°C).

C12resulting ilom the destruction of chlorinated hydrocarbons will be captured by the sodium and
potassium in the gas phase, well before this temperature.

18
 Tvpical Dioxin and Furan Emission Data

Table 3

I Dioxin 2378-isomers [ TEQ II ng/Nm3 Ing/Nm3 TEQ

2378-TCDD 1 0.004 0.004

12378-PCDD 0.5 0.037 0.018
123478-HxCDD 0.1 0.039 0.004
123678-HXCDD 0.1 0.072 0.007
123789-HXCDD 0.1 0.019 0.002
123789-HXCDD 0.01 0.089 0.001
OCDD 0.001 0.187 0.000

~ 0.036

Total Toxics Dioxins 0.446

Total TCDD 1.217
ToTal PCDD 1.931
Total HxCDD 0.811
Total iipCDD 0.073

Total Dioxins 4.479

[Furan 2378-lsomem I TEQ II ng/Nm3 Ing/Nm3 TEQ

12378-TcDF I 01 II 0.073 I 0.007 1

)12378-PCDF I 0.05 II 0.023 I 0.001 I

----- , -----
k!

1! 0.010 I 0.000
[OCDF I 0.001 h 0.050 I 0.000

~ 0.038

Total Toxic Furans 0.338

Total TCDF 3.090
Total PCDF 0.348
Total HxCDF 0.054
Total HpCDF 0.017

Total Furans 3.848

Total TEQ ~
Total Toxic CoGeners 0.784
Total Toxic Dioxins 0.446
Total Toxic Furans 0.338
Total Tetra-Octa CoGenera ~

Ratio TOC/TEQ
 2378 TEQ Emission vs ESP Temperature
Fig 7

10 1

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This then leaves the last pathway as the most probable route for D&F formation.

The optimum temperature range and location for dioxin formation is in the precipitators at 200-
350”C. Fig 7 shows some of the experimental evidence that is available.

The only way that D&F’s can be formed in the cement kiln precipitators is from catalytic activity
with the cement kiln dust with organics from the raw meal, some of which is evolved at
temperatures lower than combustion.

The reason for the optimum location is that the formation rate of dioxins is slow and typically
around 5 seconds residence time is required around 250°C to form dioxins. While the temperature
exists in the process the residence time does not.

However C12has to be present in the gas phase for dioxins to be formed. As the Clz from the RLF
is adsorbed by alkalis. The only possibility for free Clz is associated with the raw meal.

If free Clz is not available the Deacon reaction can produce it from HC1,

HC1 + Oz + Cl, + H,O

catalysed by CUC12,CUO are even carbon as the most probable.

Only up to 6 ppm of HC1 have been found at Weardale. Tests with a 0.6V0 Clz coal yielded only
2ppm. These levels are 2 orders of magnitude lower than that required to form significant levels
of dioxins due to catalytic activity at 200-350°C.

In addition the Weardale precipitators operates at around 100”C and is outside the temperature
range for a significant formation rate.

Consequently the emissions of dioxins should be low and not a flmction of the use of RLF or its
Clz content.

This has been demonstrated at Weardale where the dioxins emissions although low have been
shown to be a tl.mction of raw meal carbon and the HC1 emission to be independent of the Clz in
the fiel.

Measurements of CO at the exit of the Weardale kiln has shown that the CO level is in the range
30-50ppm at 2/3’XO0= which when compared to the stack emission to 300-700 mg/Nm3 at around
11?40oxygen indicates that the dioxins must form born the carbon in the raw meal.

This is the general situation in Europe where a survey of German and Austrian kilns has given a
range of TEQ emissions of 0.035-0.07 ng/nm3.

These figures are fairly typical, with Lepols in Ciment LaFarge recording 0.035 ng/nm3 TEQ, with
RLF firing both in the front of the kiln and over the grate.

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Ciment D’ Obourg have never measured above 0.05 ng/Nm3 TEQ except when burning a car
fragmentation waste which led to a high concentration (20000ppm) of Cu in the precipitator dust.

ENCI (Holland) in their only test recorded 0.5 ng/Nm3 TEQ using their conventional fhel mix.
However ENCI has on in line raw meal dryer which was being fired with brown coal during the
test.

5.4 Potential BCI Dioxin Problem Areas

Generally most cement works should not have any problems @h the levels of dioxins that they
emit, even with a substantial amount of carbon in the raw meal proving their ESP or bag filter
operates less than about 180°C.

However kilns such as Northfleet and Ravena could have a problem due to their figh ESP
temperature. ,,

Care needs to be taken over how the measurements are made and the results interpreted.

An outside Organisation with experience of the EPA method for the measurement of Dioxins
should be used.

Generally all results below 0.1 ng/Nm3 TEQ should be regarded as similar.

The fist target should be below O.lng/Nm3 TEQ. If above this level a secondary target could be
30ng/Nm3 Tetra-Octa.

Ifit is required for a works to reduce dioxins emissions the first step must be to reduce the inlet
temperature to the ESP to below 200”C.

If this is not sufficient and the kiln o~gen is above 2/3%, contact BCTC and ask for LA WZ?.llJ.

6. Conclusions

The formation mechanisms and reasons for the emissions of NOX, SOZ, Heavy Metals and
Dioxins and Furans have been outlined.

Suggestions have been made as to how each of these pollutants could be reduced given stricter
legislation.

The subject area is an ever moving situation and the appropriate technology is changing with
whatever limits are set. ,’

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