Volatile Elements (Cl, S, Alkalis)

in Cement Kiln Systems

Josef Waltisberg
dipl.Ing. ETH
Eichhaldenweg 23
CH-5113 Holderbank / Switzerland
josef@waltisberg.com
 1

The Chlorine Problem

Remark: Most of the bromine compounds are volatile

Behavior similar to chlorine  cycle  clinker
Waltisberg
see «The Elements Fluorine, Bromine and Iodine in a Cement Kiln»
Consulting 2
 The Chlorine Problem
Raw Meal with
Chlorine Input is not an chlorides
Emission Problem Cl Emission
but an Operation Problem negligible
of the Kiln Calciner Fuel
with chlorinated
compounds

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

2015 - Measurements in Germany (VDZ)

128 HCI concentration values from measurements of 38 rotary kilns.
74 values were below the detection limit, which ranges between 1.5
and 2.1 mg/m³ depending on the measurement.
Waltisberg
Consulting
www.vdz-online.de/en/publications/environmental-data 5
 Volatile Elements

 Alkalis, sulfur and chlorine compounds in (conventional and/or

alternative) raw materials and (conventional and/or alternative)
fuels utilized for the cement production, when present in high
concentrations, often given rise to difficulties in kiln operation
with build-up formation.

 The build-up formations cause cyclone blockages or restrictions

of the kiln inlet area so that the kiln has to be stopped for
cleaning

 Volatile Elements are:

Sulfur SO3
Potassium K2O
Sodium Na2O
Chlorine Cl

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

Chlorine Alkalis Sulfur CO2 Ca / CaO

high
Fastest Reaction KCl, NaCl
Cl + Alkalis
Cl excess Reaction CaCl2
Priority


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

Hot Meal Clinker Volatility φ

SO3 1.56 0.60 0.62
Volatile K2O 2.55 0.85 0.67
Hot Meal Na2O 0.08 0.08 0.00
cHM Cl 1.83 0.02 0.99
Clinker cKli

High Volatility of Cl
High Affinity between S and K

Waltisberg
Consulting 14
 Theoretical Enrichment (Example)

Factor ~ Concentration Hot Meal / Concentration Input

(Input = Input of Raw Meal + Fuel(s) [kgX/kg Cli])

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

Desirable value between 0.8 and 1.2; optimum 1.2

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.

 The maximum possible input of chlorine from AF depends on the

following factors:
(1. Kiln type)
 2. Input of chlorine
 3. Sulfur-cycle

 To define the maximum acceptable chlorine concentration for a

certain type of AF, the actual situation with regard to total Cl-input
into the kiln must be assessed first (balance of circulating
elements).

Waltisberg
Consulting 21
 Input Limit for Chlorine

Limits for Kilns without Chlorine Bypass

The following limits are expressed as «total input of chlorine based on
clinker [mg Cl/kg clinker]»
Total input = chlorine from the raw material and the conventional
and/or alternative fuel(s)

Cyclone preheater kiln (with or without calciner)

< ~ 300 [mg Cl/kg Clinker]
(depending on sulfur cycle, control of enrichment at kiln inlet)

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 [%])

Problem: Uncertainty of measured values!

Waltisberg
Consulting 23
 Chlorine Bypass
Reduction of Chlorine Cycle with a
Bypass Systems
A part of the gas at kiln inlet is extracted and the
enriched dust is discarded from the system

Separate stack
or connection to
main stack
Bypass

Enriched Dust Extraction

Waltisberg
Consulting 24
 Input Limits for Chlorine

Cyclone preheater kiln with bypass

Cyclone preheater kiln (with or without precalciner)
with bypass ~ < 300 [mg Cl/kg Clinker]
Additional +1 [%] bypass rate  +100 [mg Cl/kg
Clinker]
(depending on sulfur cycle, control of enrichment at kiln inlet)

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.

Light coatings: Not relevant, cleaning frequently low

Medium coatings: Regular cleaning; frequency ± once per shift
Waltisberg Severe coatings: Permanent cleaning; partly kiln stops 26
Consulting
 Volatile Elements - Guideline Values for Input

Limits for Total Input (raw meal and fuels)

(Values related to clinker)

Cl < 0.03 %  normal case, no problems

> 0.05 %  heavy clogging problems,
depending on the sulfur cycle
SO3 < 0.5 %  normal case, no problems
> 1.25 %  heavy clogging problems
K2O < 1.0 %  normal case, no problems
> 1.5 %  problems with build-ups, depending on
(molar alkali/sulfur ratio)
Na2O Little volatile
 no problems due to recirculation of Na2O

Waltisberg
Consulting 27
 6

Replacement of Coal
by Petcoke and Tires

Waltisberg
Consulting 28
 Influence of Alternative Fuels on Alk/S-Ratio

Partial Replacement of Coal with Waste Tires or Petcoke

Kiln: Preheater Kiln; Heat Consumption: 3.5 [MJ/kg Cli]

CV K2O Na2O SO3

[MJ/kg] [%] [%] [%]
Raw Meal 0.40 0.10 0.50
Coal 28.0 2.30 0.70 2.00
Petcoke 30.0 0.50 0.10 10.00
Tires 28.0 0.07 0.03 2.50

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

Input: 1.3 [t/h]

 4.0 [%]

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

Blue: without plastic

Red: with plastic
~ 0.8 [%] Cl
(calculated example)
Green: with plastic
< 0.5 [%] Cl

Information from Plant:

without plastic: Low tendency to build-ups; cleaning every
second/third day
with Plastic: Significant higher tendency to build-ups;
red point: cleaning at least every shift
Waltisberg
Consulting 36
 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

 Calculated Quantity: 1.3 [t/h]

Production: 2’800 [t/day] (116.7 [t/h])

 Cl input with plastic:

Input with 0.8 [%] in plastic  178 [gCl/t clinker]
Input with 0.5 [%] in plastic  145 [gCl/t clinker]

Waltisberg
Consulting 37