JW DZ 02a e
JW DZ 02a e
JW DZ 02a e
Josef Waltisberg
dipl.Ing. ETH
Eichhaldenweg 23
CH-5113 Holderbank / Switzerland
[email protected]
1
Fuel
with chlorinated
compounds
Problem zone
Accumulation
Blockages
Waltisberg
Consulting 3
2
Emission of HCl
Volatile Elements
Build-up, Blockages
Waltisberg
Consulting 4
Emission of HCl
Waltisberg
Consulting 6
The Chlorine Problem: Build-Ups
Severe Build-Ups
at Kiln Inlet
Waltisberg
Consulting 7
Example of Enrichments in Kiln System
Problem: High Enrichment at Kiln Inlet (Hot Meal)
Kiln Feed Hot Meal Clinker
L.O.I. [%] 34.8 4.8 0.35
Analysis L.O.I. free [%]
SiO2 20.9 20.5 21.0
Al2O3 4.7 4.2 4.9
Fe2O3 3.1 3.0 2.9
Enrichment of Hot Meal CaO 65.2 61.2 64.9
MgO 2.5 2.3 2.2
Factor ~ 16 SO3 0.10 1.56 0.60
K2O 1.08 2.55 0.85
Na2O 0.09 0.08 0.08
TiO2 0.28 0.28 0.3
Mn2O3 0.06 0.06 0.04
P2O5 0.08 0.11 0.17
Factor ~ 180 Cl 0.01 1.83 0.02 *)
Total 98.1 97.7 98.0
Waltisberg
Consulting *) Detection Limit: ~ 0.005 [%] 8
3
Volatile Elements
Affinity Order,
Cycles and Enrichment
Waltisberg
Consulting 9
Circulation of Volatile Elements
Depending on the degree of volatility, the circulating
elements evaporate in the sintering zone of the
cement kiln and are carried by the gases to colder
zones, where they mainly condense on the meal and
partly also on the surrounding walls.
Afterwards they return with the meal into the sintering
zone where they partly re-evaporate depending on the
degree of volatility. This repeated process through the
kiln leads to the establishment of internal cycles.
Finally the cycles reach equilibrium so that the output
of circulating elements is equal to their input by the
raw materials and the fuels.
Waltisberg
Consulting 10
Volatile Elements – Table of Affinity
Alkali excess K2SO4
Reaction with Sulfur Na2SO4
Alkali Reaction K2CO3
excess Na2CO3
Sulfur Reaction CaSO4
excess
Waltisberg
Consulting 11
Typical Chlorine Profile (Spot Measurement)
Emission at Stack:
< 2 [mg/m3N]
336 [°C] 0.01 [%] Cl
Cl Concentration
325 [°C] in the Meal Tubes
0.03 [%] Cl
514 [°C]
504 [°C] Build-ups
0.08 [%] Cl
KCl
823 [°C]
811 [°C]
0.42 [%] Cl
1094 [°C]
1.45 [%] Cl
Cyclone
aryWaltisberg
Kiln Preheater
Consulting 12
4
Volatility of
Alkalis, Chlorine and Sulfur
Waltisberg
Consulting 13
Volatility of Elements
SINTERING ZONE
cKli
1
Fuel(s) cHM
High Volatility of Cl
High Affinity between S and K
Waltisberg
Consulting 14
Theoretical Enrichment (Example)
Waltisberg
Consulting 15
Volatility of Chlorides
The chlorides liberated during heating of the material and
combustion of the fuel react with the alkalis to form alkali chloride.
This reaction takes place either in the charge material or, after
vaporization, in the kiln gas.
At a temperature level of 1200 to 1300 [°C] the chlorides (KCl,
NaCl, CaCl2) are already volatilized to a great extent. At sintering
zone temperatures they are almost entirely volatilized so that the
total volatility factor is approx. 0.97 to 1.00, i.e. only a small
portion leaves the kiln with the clinker.
Waltisberg
Consulting 16
Molar Sulfur-Alkali-Ratio
Basically, the Alk2SO4 are little volatile, whereas the CaSO4 is
highly volatile. Therefore the most important criteria for the total
sulfur volatility is the molar ratio between the alkalis and the sulfur
itself, corrected by the chlorine:
K 2 O Na 2 O Cl
Alk
94 62 71
SO 3 SO 3
80
Waltisberg
Consulting 17
Molar Alkali-Sulfur-Ratio
The desirable value for the alkali-sulfur-ratio is 1.2 (range
between 0.8 and 1.2).
If there are sufficient alkalis available to combine with the total
sulfur input (from raw materials as well as from the fuel), the
total volatility for the sulfur is = 0.3 to 0.5 low
enrichment factor.
Waltisberg
Consulting 18
Molar Alkali-Sulfur-Ratio
If there is a surplus of sulfur over the alkalis, the highly volatile
CaSO4 is formed. Its volatility is approximately = 0.9, but
can increase up to = 1, depending on the operating
conditions of the burning process High enrichment
possible.
Waltisberg
Consulting 19
5
Guideline Values
for the Input of
Alkalis, Chlorine and Sulfur
Waltisberg
Consulting 20
Chlorine – the Most Critical Element
Chlorine is by far the most important circulating element with regard
to Alternative Fuel (AF) utilization.
Waltisberg
Consulting 21
Input Limit for Chlorine
Waltisberg
Consulting 22
Maximum Input - Example
Cl-Limit: 300 [g/t Cli]
Cl Content Raw Meal: 100 / 150 [g/t]
Sulfur Cycle: negligible
Conventional Fuel: negligible
Raw Meal: 100 [g/t] (0.010 [%]) Raw Meal: 150 [g/t] (0.015 [%])
Separate stack
or connection to
main stack
Bypass
If the bypass dust is mixed into the cement, the maximum Cl limit of
the cement (usually Cl < 0.1%) has to be respected.
Waltisberg
Consulting 25
Chlorine and Sulphur
The indicated limits depend also from the sulphur input.
From experience it is known that certain concentrations in the hot
meal should not be exceeded. The following chart shows the
relationship between chlorine and sulfur enrichment.
Waltisberg
Consulting 27
6
Replacement of Coal
by Petcoke and Tires
Waltisberg
Consulting 28
Influence of Alternative Fuels on Alk/S-Ratio
Cl negligible
Waltisberg
Consulting 29
Influence of Alternative Fuels on Alk/S-Ratio
Example #1; Replacement of Coal with Waste Tires
No significant change of Alk-SO3-Ratio and Sulfur Input
No influence on sulfur cycles can be expected, if there is enough
oxygen in the back-end-zone
Waltisberg
Consulting 30
Influence of Alternative Fuels on Alk/S-Ratio
Example #2; Replacement of Coal with Petcoke
Significant change of Alk-SO3-Ratio Over-sulfurization
Increase of sulfur volatility with increasing amount of petco
Input of more than 15 - 20 [%] petcoke cause severe kiln problems
Counteractions: Limitation of petcoke; correction of raw material, …
Waltisberg
Consulting 31
7
Example of
Plastic Combustion in a Kiln
Waltisberg
Consulting 32
Example: Plastic Combustion
Conservative
Assumption
because of Sulfur
Input calculated
5.0 [%]
2800 [t Cli/day]
~ 1.6 [t Plastic/h]
Waltisberg
Consulting 33
Alkali-Sulfur-Ratio
Non essential
change of Ratio
Waltisberg
Consulting 34
Plastic Combustion - Volatility
cCli
1 cCli cInput
cHM
Without Plastic:
Chlorine: 0.009 [%] Input (calculated)
0.42 [%] Hot Meal (measured)
0.979 Volatility
Sulfur (SO3): 0.842 [%] Input (calculated)
1.53 [%] Hot Meal (measured)
0.450 Volatility
With Plastic:
Chlorine: 0.018 [%] Input (calculated)
1.03 [%] Hot Meal (measured)
0.983 Volatility
Sulfur (SO3): 0.836 [%] Input (calculated)
1.65 [%] Hot Meal (measured)
Waltisberg 0.507 Volatility
Consulting 35
Plastic Combustion - Changes in the Hot Meal
Counteraction:
Test with plastic with Cl-content < 0.5 [%]
Less build-ups; operation acceptable
no detailed investigation available
Waltisberg
Consulting 37