GLOBAL TRENDS IN THE CEMENT MAKING PROCESS UNITECR 2009, Salvador - Brazil

Adam A. Wajdowicz October 2009

Challenges of the cement global industry

Reduce energy consumption

Increase the use of alternative fuels

Gt26

Use of alternative raw materials without changing clinker quality- materials recycling

Reduce emissions of CO2 setting targets to reduce greenhouse gas emissions

Great concern how to protect the environment .

Strong research in the sphere of sustainability

MARKET ENVIRONMENT & GLOBAL CRISIS

Some countries have been badly affected like USA, Ireland, Spain, UK.
Africa and Middle East lost 10% in some countries

In central Europe the loss of production varies from 10 to 40% in some countries.
Many old wet process kilns have been discontinued for ever.

Whoever will be not able to reach 70% of substitution of energy source via alternative fuels and raw materials will be not competitive.
On average 40% substitution is a reality in Europe, Asia, North America and South America. Right now many European countries are targeting 88% substitution rate.

Present reality
Simultaneous grinding of coal and pet coke lead to a variable grain size once the Hardgrove index is different. Coarser grains of pet coke with more than 90 micron sieve tend to burn at very upper transition zone.
This causes the appearance of double or triple flame affecting coating distribution and the kiln thermo-chemical gradient. Coal ash has to be ground sufficiently fine and injected sufficiently far into the kiln to make sure that it will be incorporated into the raw meal. Coarse ash particles and those projected insufficiently far into the kiln fail to combine, giving higher levels of free lime . Liquid waste with variable amounts of water and varying heat value make the flame to be non predictable and impinging on the refractories, index Burning of chlorinated plastics and solvents without continuity. Sudden increase in burning zone thermal load (new coolers, new burners) Variable degree of precalcining at the kiln inlet

Impact on the process

More frequent ring and buildup formation

Imbalances in Sulfur/alkali ratio Frequent need to change the in kiln rotational speed. Increase in the number of cold stoppages Low alkali clinker, oil well clinker, off-white clinker, etc More wear at kiln tire stations specially if clinker is dusty.

Very difficult to specify the right brick as someone has to decide if the brick should encourage coating development or avoid it!
Variable coating development at the area of upper transition tire is a headache. This condition may cause the temperature to be hotter on one side of the shell than the other. This causes stress and torsional displacement of the refractories.

More impacts on the process

REPLACEMENT OF TRADICIONAL FUELS LIKE NATURAL GAS, PET COKE,

OIL,

RESIDUAL COAL, PAPER, PLASTICS, MEAT, BONE MEAT, BATTERY CASINGS, USED
LUBRICANTS, WASTE SOLVENTS, SHREDDED TIRES, MUNICIPAL GARBAGE, ETC. THE USE OF ALTERNATIVE FUELS AT THE RISER DUCT IS MORE DIFFICULT IN THE SATTELITE COOLER KILNS ONCE THE DRAFT AND OXIGEN COULD BE NOT ENOUGHT

TO BURN THEM PROPERLY. USUALLY IS LIMITED TO 20-25% OF SUBSTITUITION.

LONGER FLAMES AND LOW HEATING VALUES REQUIRE MORE FUEL AT THE BURNING ZONE TO MAKE SURE THAT FREE LIME IS LOW. THAN THERMAL LOAD EXCEEDS 5 x106 Kcal/m2.h. USUALLY IT IS HARD TO GET A STABLE COATING.

ROTARY KILN ZONES

BURNING ZONE

UPPER TRANSITION

LOWER TRANSITION

EXCELLENT FLEXIBILITY HIGH RESISTANCE AGAINST INFILTRATION ALKALIES SALTS HIGH RESISTANCE AGAINST CHEMICAL CORROSION BY CLINKER LIQUID PHASES AND SO3 AND OR ALKALI SALT VAPORS.

Different kiln zones and types of wear

ZONE 1: POTASSIUM CHLORIDE INFILTRATION, CONDENSATION

ZONE 2: POTASSIUM SULFATE INFILTRATION, CONDENSATION

ZONE 3: UNSTABLE COATING, BRICK EROSION, MECHANICAL STRESS ZONE 4: PEAK TEMPERATURE, CLINKER MELT INFILTRATION, REDOX, COATING PULL ZONE 5: FLAME IMPINGEMENT, UNSTABLE COATING, BRICK EROSION, MECHANICAL ZONE 6: ABRASION, THERMAL SHOCK, ALKALI INFILTRATION, BRICK RETAINER

MA

MA

MgO
MA

MgO
MgO MgO

350C

MA

MgO
MgO MgO

1450C

DAY AND NIGHT CaO TENDS TO SATURATE THE CERAMIC BRICK MATRIX

MA

MA
MgO

KCl Alkali

MAJOR MINERALOGICAL PHASES & ACCESSORY PHASES

CLINKER

BASIC BRICK
MAJOR

C3S C2S

MgO MgO.Al2O3 DOLOMA ZrO2 Hercynite C2S, C3S M2S, CMS, C3MS2 C12A7 3CaO.3Al2O3.CaSO4 MgO.Fe2O3 K2Mg2(SO4)3 K2SO4 KCl, NaCl Phase Q-C20Al26Mg3O68

C3A C4AF CaO ALKALI, Sulfates Fluorine Etc.

ACCESSORY

LIME SATURATION FACTOR

KLL DEVELOPED AN EQUATION THAT DEFINES THE MAXIMUM QUANTITY

OF LIME COMBINED WITH SiO2, Al2O3, AND Fe2O3

THEN LSF SHOWS THE LIME EFFECTIVELY SATURATED AT 1450C IN A KIND OF FROZEN EQUILIBRIUM FREE LIME IS THE LIME THAT CANNOT BE COMBINED. IF FREE LIME IS TOO HIGH IT WILL BE AVAILABLE TO SATURATE REFRACTORY MINERALS TO DEVELOP NEW SILICATES. THIS IS THE MATRIX

CORROSION.

TYPICAL KILN CONSTRAINS

LIQUID PHASE CORROSION THERMAL OVERLOAD THAT DRASTICALLY REDUCES LIQUID PHASE VISCOSITY LIQUID PHASE INFILTRATION HIGH KILN SHELL TEMPERATURE BUT WITH CONDITIONS TO DEVELOP AND KEEP A SOUND AND STABLE COATING

HIGH KILN SHELL TEMPERATURE WITHOUT ANY CHANCE TO GET COATING

MECHANICAL STRESS - OVALITY - POOR ALIGNMENT ALKALI & SULFATES ABRASION RESISTANCE THERMAL LOAD REDUCING ATMOSPHERE SHIFTING CLINKER TYPES 2 TO 3 TIMES PER MONTH

TYPICAL CONSTRAINTS IN ROTARY KILNS

WHERE TO WORK OUT

SELECTION OF RAW MATERIALS EXEMPT OF B203, Fe203,
& SiO2 REDUCED, SMALL AVERAGE DIAMETER OF PORESCORROSION RESISTANCE OF THE SPINEL GRAIN LOW PERMEABILITY

BRICK PROPERTIES

LIQUID PHASE RESISTANCE

THERMAL SHOCK

SELECTION OF RAW MATERIALS THAT FAVOUR THE

COATING ADHERENCE -REDUCE THE SURFACE TENSION CHOICE OF RAW MATERIALS THAT REDUCE THE THERMAL CONDUCTIVITY CHOICE OF SECUNDARY AGGREGATES WITH LOW E.M.

RESISTANCE

THERMAL CONDUCTIVITY

HIGH COLD CRUSHING STRENGTH

HIGH REFRACTORINESS LOW Fe2O3 CONTENT

ALKALI RESISTANCE

PERMEABILITY

ELASTIC MODULUS

COATING BEHAVIOUR

How do you see this graph ?

Very interesting but my eyes can only see

CLINKER

CALCINATION

UTZ

BURNING

LTZ

Raw mea l

Limestone Clay Quartz CA C12A7 C2S Free lime Spurrite

Free lime C2S C2F C3A C4AF C2AS LP1338C

C3S C2S C2AS C3A C4AF Free lime LP1450C

C3S C2S C3A C4AF Free lime

Clinker

What are the most outstanding wear Mechanisms at that part ?

Main facts: Temperature from 50 to 950C; Decarbonation is mostly concentrated in the static preheater; Presence of alkali vapours; If CO2 and SO2 are not removed at right time then there is a risk to develop middle kiln rings; Brick melting if there is double flame problem due to unburnt fuels Kiln shell corrosion
Then the ideal refractories should have: Low permeability; Excellent resistance to alkali attack; Non wetting properties Low thermal conductivity Al203 contend around 35% at preheater And special fireclay alkali resistant into the kiln

Limestone Clay Quartz CA C12A7 C2S Free lime Spurrite

What happens nowadays at upper transition zone? UTZ If raw meal has big variability coating is unstable The position of the appearance of first liquid phase Fuel varies according to the fuels type set up. VA Kiln shell temperature could vary from 360C up to 410C If coating is unstable. As a consequence an induced high kiln ovality maybe present. Risk of brick spiralling. Serious and unpredictable alkali salts infiltration

Free lime C2S C2F C3A C4AF C2AS LP1338C

Brick properties required:

Low permeability; Capability to absorb as much as possible alkali salts without the risk to exceed the maximum acceptable elastic modulus

What does it mean BURNING ZONE ? MAIN WEAR MECHANISMS:

Thermal load Clinker liquid phase corrosion Flame impingement Abrasion Unstable coating Reducing atmosphere

C3S C2S C2AS C3A C4AF Free lime LP1450C

BASIC BRICKS THAT CAN OFFER:

RESISTANCE TO CLINKER LIQUID PHASE CORROSION CAPABILITY TO DEVELOP COATING THERMAL SHOCK RESISTANCE LOW AVERAGE PORE SIZE RESISTANCE TO THE CLINKER TYPE SHIFTING HIGH THERMAL LOAD WHENEVER PRODUCING HARD TO BURN CLINKERS

LOWER TRANSITION ZONE Clinker abrasion; Mechanical stress Shifting coating MECHANICAL STRESS DUE TO THE TYRE STATION WRONG DESIGN OF RETAININIG RINGS THERMAL LOAD ALKALI ATTACK WITH KILNS WITH HIGH EFFICIENCY COOLERS-SECONDARY AIR CLOSE TO 1200C ALK BASIC BRICKS MUST HAVE:
C3S C2S C3A C4AF Free lime HIGH ABRASION RESISTANCE RESISTANCE TO CLINKER LIQUID PHASE CORROSION VERY LOW AVERAGE PORE SIZE LOW GAS PERMEABILITY LOW ELASTIC MODULUS & HIGH FLEXIBILITY

MAJOR PROBLEMS CAUSED BY THE THERMO-CHEMICAL GRADIENT DISPLACEMENT

GT23

RET

LP 1338C

NO COATING

Conclusions

The present reality requires more research of refractories resistant to alkali vapors, sulfates and many other minor elements like fluorine, zinc, etc. Special refractories based on lime and MgO to resist thermal overload when shifting fuels or clinker types. Numerical simulation to determine the thermal mechanical behavior for refractories for cement kiln applications. Development of refractories with lower thermal conductivity to reduce thermal losses.

THANK YOU VERY MUCH FOR YOUR TIME!

New Challenges for Refractories with 2D and 3D Alternate Fuels

60
Sewage Waste Municipal Waste

Relative Specific Fuel Consumption [%]

50

Zinc
40

Animal Meat / Bone / Fat Plastic

30

Phosphate Chlorine Chlorine / Sulphate

Pulp / Paper / Cardboard

20

2D and Other Industrial 3D Waste

Solvents Waste Oil

10

Chlorine / Fluorine Sulphur / Zinc

1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007

Tyres

Year

RT2

Distribution of Thermal Energy Consumption of Alternate Fuels - Germany

FREQUENT FUEL CHANGES

COKE

C/H
BUNKER DIESEL WDF H2 CH4

COAL

GAS

RT17

EMMISSIVITY

Example big raw meal variability 30 running days

Rt 17

Example of mag-spinel after one year at lower transition zone of a kiln burning plastics and some industrial residues
Distance from the cold face (mm) PHYSICAL PROPERTIES Bulk Density (g/cm) Apparent Porosity ( % ) Cold Elastic Modulus ( GPa ) Coating 85 -88 KCl MgO NaCl Intermediate face 2 60 - 85 3,15 2,1 MgO MA NaCl CaSO4 Intermediate face # 1 30 - 60 3,16 3,5 155,9 MgO MA CaSO4 NaCl Cold Face 0 - 30 3,00 10,9 114,6 MgO MA KCl NaCl CaSO4 CaCO3 0,34 0,12 0,01 5,55 0,02 0,48 0,10 1,24 87,40 0,55 1,79 0,00 1,28 0,00 1,46 11,06 -0,29 1,73 < 0,40 5,00/8,00 < 0,60 < 1,00 89,00/93,00 TDS new brick 2,90/3,02 14,0/17,0 20/40

XRD

CHEMICAL ANALYSIS - PHILIPIS MagiX PRO L.O I SiO2 TiO2 Al2O3 Cr2O3 Fe2O3 MnO CaO MgO Na2O K2 O P2O5 SO3 ZrO2 Chlorides CaO / SiO2 Molar Ratio ASM AE

0,19 0,17 0,01 5,23 0,01 0,60 0,10 0,73 82,89 0,34 5,61 0,00 0,28 0,00 4,03 4,59 -0,02 4,04

0,17 0,12 0,01 4,79 0,01 0,44 0,10 1,72 84,22 0,40 3,78 0,00 1,51 0,00 2,90 15,34 -0,16 2,89

Rt 19