Alternative Fuels in Cement Industry
Alternative Fuels in Cement Industry
Alternative Fuels in Cement Industry
Alternative fuel
DI FRIEDRICH WILLITSCH DR. GERNOT STURM PMT-ZYKLONTECHNIK GMBH KREMS, AUSTRIA PROF. FRIEDRICH WURST PROF. THEODOR PREY UNIVERSITY OF VIENNA
PMT-Zyklontechnik GmbH
Alternative fuel
4 STORAGE, DOSING AND FEEDING OF FUELS .............................................. 11 4.1 STORAGE ........................................................................................................... 11 4.2 DOSING AND FEEDING ......................................................................................... 12 5 BURNER CONCEPTION AND COMBUSTION.................................................. 15
6
6 CONTROL AND ANALYZING............................................................................ 16 6.1 INITIAL CONTROL ................................................................................................ 16 6.2 INTERMEDIATE CONTROL ..................................................................................... 17 6.3 OVERVIEW OF ANALYZING AND LABORATORY APPARATUSES FOR QUALITY CONTROL OF ALTERNATIVE FUELS:............................................................................................. 17 7 INFLUENCE ON EMISSION............................................................................... 20 7.1 EMISSION OF BALANCE COMPLIANT ELEMENTS ...................................................... 20 7.2 EMISSION OF NON NON BALANCED TRACE ELEMENTS ORGANIC COMPOUNDS ........ 21 8 INFLUENCE OF ALTERNATIVE FUEL IN CLINKER PRODUCTION ............... 23 8.1 8.2 8.3 8.4 GENERAL ........................................................................................................... 23 LOW VOLATILE METALS ...................................................................................... 23 SEMI- LOW VOLATILE METHOD ............................................................................ 24 HIGH VOLATILE METALS ..................................................................................... 24
PMT-Zyklontechnik GmbH
Alternative fuel
PMT-Zyklontechnik GmbH
Alternative fuel
achieved. Depending on the type of alternative fuel used, a substitution up to 80% can be achieved in some case up to 100%. Due to the use of alternative fuel in the clinker production the cement industry takes some important disposal functions at the same high economical stakes. The claim of waste industry about destroying of detrimental organic substances in controlled processes as well as the avoidance of detrimental residue (ash, slag) due to the storage of heavy metal in clinker components in the lowest, most innocuous concentration will be fully covered. Emphasizing Advantages by using Alternative Fuels: 1. Reduction of CO2- Emissions (Kyoto-target):
-
Dumping of thermal utilizing waste the active greenhouse effect will occur By combustion in combustion plant additional CO2 emission occurs.
2. Cost reduction of PZ-Clinker production due to using inexpensive fuel. 3. Preservation of resources lower use of fossil nonrenewable fuel 4. Reasonable secondary use of material 5. Residue free combustion due to not existing ash, soil and sewage 6. No significant change of emissions 7. Hazardous substances will be destroyed due to the process high temperature level, long gas residue time, alcalic combustion material, counter flow principle and oxidizing atmosphere 8. High thermal efficiency 9. Fulfillment of substantial dump disposal 10. High yielding ecological balance
PMT-Zyklontechnik GmbH
Alternative fuel
water as moisture organic components mineral components responsible for the ash content
The following schedule shows currently used and most conventional alternative fuels in European Cement Industry.
significant contamination
Pb, Zn, CI
according to the humidity according to the 11 to 18 humidity 2600 to 4300 ca. 25 ca. 6000 to 7000 according to the blend to 29 6900 humidity <10% -22 according to the humidity to 8 12 to 16 humidity < 10% 5300 according to the humidity 2000 3100 to 3800
In that schedule the possible contamination is shown by different elements, potential moisture content and the calorific values. The properties of the elements at feeding as combustion fuel in the kiln system has to be evaluated depending on the level of contamination. The question is, which transfer and in which form and value could that be done? Typical properties of the elements: Transfer principal into the Clinker-mineral-elements clinker Low volatile metals sulfur Aluminum, Calcium, Zinc, Fuel Iron, Lead, Silicium, Chrome, Nickel,
PMT-Zyklontechnik GmbH
Alternative fuel
General transfer into the Volatile metals (as long as Mercury, non incinerated exhaust air used without additional organics, meal Thallium, Mercury (partly),Cadmium (partly) Sulfur of raw filter) combustion gases Transfer into filter dust and Semi volatile metals external circulation via raw meal. As long as periodical release of circulation due to additional grinding to the cement Absorption due to raw meal Halogene, Alkalis in the cooler upper part. Recuperation in the hot kiln area. Internal circulation. Due to implementation of a By-pass elements disposal. In some case it is possible to compare some analysis of the used combustion fuel to the used alternative fuel and raw meal which has a lot bigger mass flow (raw meal/fuel = approximately 16:1) to give a ballpark figure about reaction. system for it is possible to discharge those external Chlorine, Kalium, Natrium residuals & are
PMT-Zyklontechnik GmbH
Alternative fuel
PMT-Zyklontechnik GmbH
Alternative fuel
PMT-Zyklontechnik GmbH has come to know how to meet and match the requirements for conditioning of alternative fuels in cement industry, developed according to the type of fuel the required technology and equipment. The conditioning functionality at all operation is running mechanically and under ruled hygienic conditions .
3.1 WPP-OPERATION
In WPP- operation (Wood-preparation-Process) contaminated wood is separated of affecting contents and crushed -. depending on the scope of application in clinker processing in accordance to the particle size (primary- and secondary combustion). For using at primary conveying, a particle size of 6mm has shown as optimal size for combustion.
3.2 TPP-OPERATION
The TPP-operation (Tire-Preparation-Process) is designed for crushing of plastic, tires and plastic-like materials and plastic, as for separation of whole tires and the gravimetric dosing of that material to the kiln system too.
scan conveyor
Scanning and separation of non suitable tyres Dosing of tyres and rubber pieces
Double flap system with Pneumatic flaps
Rotary kiln
PMT-Zyklontechnik GmbH
Alternative fuel
3.3 PPP-OPERATION
The PPP-operation (Plastic-Preparation-Process) This processing is to prepare of all types of plastic, textiles, paper, composite materials, etc. contaminated with metal, glass, and minerals mechanically fully separated and prepared to fuel.
Preparation of plastic and substance mixture
before
after
For the use in primary combustion, the particle size of 10 mm edge length has shown to be optimal for higher dosing rates Combustion of bigger sized plastic material performs at entrance into the high temperature area of the flame a ball-shaped profile instantly, due to the material structure. (decreasing of surface). The reason is to avoid a too fast burn-off jeopardy of burning out at the clinker bed creating of reducing condition). The best and most economical solution to produce particles with a size of about 10mm is the use of high speed crushers. Disturbance variables have to be avoided. Pmt-Zyklontechnik GmbH has developed a special processing for this purpose.
PMT-Zyklontechnik GmbH
10
Alternative fuel
3.4 MTP-OPERATION
The MTP-operation (Mechanical-Thermal-Process) is a patented process for separation of high energy components (plastic, paper, textiles, organic material etc.) moisture and highly affecting components as metals, glass and mineral materials.
That process provides stable operation with the above mentioned material, additional some increase of bacteria and nucleus is prevented. Either no emission loss in this process. The thermal fraction is used in the PPP-process. The process was tested in order to research and develop all pertinent measuring concerning affecting emission and vitiation.
This type of process provided fuels containing a calorific value of more than 20 MJ/kg .
Waste Preparation and Gas Flow
Heat exchanger Waste heat Exhaust air fresh air Dryer off gas (polluted) Precrushing
Element As Sb Pb Cd Cr Co Ni Hg TI V Zn Sn Humidity CL HU unit [mg/kg] [mg/kg] [mg/kg] [mg/kg] [mg/kg] [mg/kg] [mg/kg] [mg/kg] [mg/kg] [mg/kg] [mg/kg] [mg/kg] [%] [%] [J/g]
Plant Material
Suck off air Domestic waste
To central burner
PMT-Zyklontechnik GmbH
11
Alternative fuel
Problems of storage
1. Organic content - Odour - Bacteria/ growth of mould - Development of heat - Solidification 2. Humidity 3. Jamming 4. Voluminously big storage space 5. Not a nice sight 6. Contamination
PMT-Zyklontechnik GmbH
12
Alternative fuel
The dosing of solid alternative fuels requires materials without property of jamming content during the feeding and dosing operation. In this case moisture is the significant role.
PMT-Zyklontechnik GmbH
13
Alternative fuel
Always keep a close look to design and construction of the feeding equipment. At pneumatic feeding it has to be assured that the conveying air capacity is as low as possible. (cooling the flame shape, NOx). Furthermore the wiring to the burner is very important as well as abrasion property of the conveyed materials has to be controlled.
Waste Oil Preparation Domestic Waste Preparation Main burner Plastics Preparation Kiln entrance riser duct
Waste Oil Sewage sludge Domestic Waste Industr. Plastic Waste Preseparated Plastics Animal Meal
Precalciner
4.2.2 DOSAGE AND FEEDING OF PLASTIC, PAPER, TEXTILES AND MATERIAL MIX
Plastic, Paper and textiles are conveyed to the main burner either mixed or separated (primary combustion), or to the secondary combustion. An Advantage is, that the material is conveyed from an intermediate bin over a weigh-belt feeder and rotary gate, by using compressed air, to the burner. This system is simple designed and simple to maintain. At designing you have to be aware to keep the requirement for compressed air as low as possible. The operation of combustion is controlled as same by using conventional fuel with conventional exhaust air components.
PMT-Zyklontechnik GmbH
14
Alternative fuel
prereservoir
dosing reservoir
Rotary valve
fan
To the burner
PMT-Zyklontechnik GmbH
15
Alternative fuel
Swirl setting device with scale Primary air damper Outer jacket tube Flexible swirl device Nozzle outstream system
Flexible swirl setting device for primary air (patent no.: 0642645)
Primary air Coal (Petcoke) Solid waste Diesel oil gun Waste oil gun
Burner nozzle section view
Refractory Primary air Secondary fuel
PMT-Zyklontechnik GmbH
16
Alternative fuel
achieve and guarantee legal emission limits at burning avoid clinker affecting vitiations as for instance Chlorine or Heavy Metals maintain preparation costs of Alternative Fuels as economically as well, even for elimination of non specific material
In order to share an effective Initial Control, first it is pertinent to elaborate Alternative Fuel specifications. The elaboration of that specification has to be based on internal and external terms and conditions. External Guideline: Enacted regulations from proper authority due to laws and some other regulation. Internal Guideline: Guideline for production and Quality Management according to quality management of clinker or respectively of cement, especially for instance chlorine restriction, or maybe guidelines by lobby. That specification is specifically nationwide and can vary. Tasks of Initial Control: At receiving of the material on site, random samples are taken to check homogenization of material. Mode and method of control as well as the number of random samples, the bulk in total to be analyzed, depend on the kind of fuel. Those controls are generally to be committed and ruled with the proper authority mutually.
Type of Control System: visual testing - based on the operators level of experience chemical analysis physical condition analysis
PMT-Zyklontechnik GmbH
17
Alternative fuel
The samples are provided to the internal laboratory, while samples are held back for processing. If the analysis show all criteria will be fulfilled, the held-back samples are forwarded to the bulk storage either spaciously or by allocation. If all criteria will not be fulfilled, all material will go back to the supplier who has to take all expenses for hauling.
6.3 OVERVIEW OF ANALYZING AND LABORATORY APPARATUSES FOR QUALITY CONTROL OF ALTERNATIVE FUELS:
The checkup of the Alternative Fuel properties within the scope of Quality Control Criteria you find beside some physical parameters, such as moisture content, calorific value and granulometric distribution and some other connoting elements approved by cement industry. In order to fit all requests as well, the following equipment is absolutely pertinent:
-
Drying closet (105C) to dry the samples Checker or groomed divider (various width of gaps) to create representative sub-samples. Laboratory jaw crusher to prepare the finished material starting at 1 m up to 10 m maximum sized granules Vibratory disc mill for sample grinding to the degree of fineness of analysis Ultra-centrifugal ball mill: to crush all organic material as plastic, animal meal, wood (freeze grinding process) Apparatus for sampling of flue-gas, for sampling of clean gas to evaluate the chlorine and fluorine content in clinker- rotay kiln waste gas
PMT-Zyklontechnik GmbH
18
Alternative fuel
Exploration Method:
-
classic and chemical exploration method as Sadoexploration, nitrohydrochloric acid. Device to provide molten pearls, forward samples into a glass-matrix (Lithiumtetraborate) with X- ray fluorescence analysis Molding die to process briquettes out of pulverized material for X- ray fluorescence analysis Microwave- Exploration equipment for hard decomposing material, acidic decomposition, especially concerning heavy metals and all cations. Bomb- Exploration for all volatile anions.
Various drying closets (40 250C) to prepare samples and determine moisture content High output muffle furnace (500 1100C) for incineration of organic samples and determination of ignition loss Analytical balance Device for providing clean water to analyze trace elements by the use of ICP Analyzer mainly to support both classic and wet-chemical methods PH Ionic meter, pH value, fluorine, chlorine, Titroprocessor for chlorine Photometric apparatus to determine all methods photometrically, even for Manganese, Chrome, etc. CS Analyzer for sulphur and carbon (TOC an carbon Dioxide) X- Ray Fluorescenic Analyzer for wide spread range of heavy metals, but so called Light-elements starting at Hydrogen up to Oxygen. All elements, especially heavy metals within the range of 10 ppm and below sub- quantitatively. ICP Plasma 400 for most of all cations within a range of trace elements up to as much as approx. 1 ppm, but Thallium an Tin at limits of detection of approx. 10 ppm.
6.3.2
Calorific Meter Gauge to determine the gross calorific value and to calculate the net calorific value automatically. Screen and various screen plates to determine particle distribution within the coarse of feed to screen
PMT-Zyklontechnik GmbH
19
Alternative fuel
Moisture Incineration Lower calorific value Higher calorific value Chlorine Heavy metals as: Arsenic, Antimony, Lead, Cadmium, Cobalt, Nickel, Mercury, Titan, Vanadium, Zinc and Tin
PMT-Zyklontechnik GmbH
20
Alternative fuel
7 INFLUENCE ON EMISSION
Analysis and evaluation off the influence by using Alternative Fuel on emission, on one hand we have to deem and match with balanced elements, on the other hand to consider organic trace elements within cleangas, which can result out of non- fully thermal- oxidizing destruction, caused by charged compounds within the fuel as well as created organic structures within the down cooling flue gas.
PMT-Zyklontechnik GmbH
21
Alternative fuel
Mercury in clinker processing is deemed as critical element due to its higher volatility. Referring to measuring for evaluation and material flow analysis, we can conclude that the transfer turns into the dust loaded rawgas to nearly 100%, which are split to precipitator dust and to dedusted cleangas depending on temperature and process from 40 60%. A higher given factor for limitation of Hg-charging into the kiln system for this element at initial controlling, respectively the waste fraction containing higher Hg-content without additional Hg-separation referring to cleangas, can be expelled from Alternative Fuel segment. Precise data of conditioned secondary fuel (high calorific value) shows emission concentrations from 0,003 and 0,018 mg/Nm - corresponding to enacted emission regulation. Chlorine content of fuel is to be processed in the hot incineration zone first to HCl causes with alkalis an inner concentrating circle, which can be released partly due to By-pass discharge. The input value of Alternative Fuel gets some more important, regarding Chlorine and the accumulation of chlorine in the precipitator dust can be measured. Due to alkali atmosphere and processing parameters it is not very likely getting HCl released to higher concentration in cleangas. Emission concentration in bag precipitator dedusting is around 4mg HCL/Nm, but parts of that content of Chlorine occurs as Ammonium- or Alkalichloride.
PMT-Zyklontechnik GmbH
22
Alternative fuel
For formation of chlorine organic compounds while fluegas cooling off in clinker process, the existing condition is pretty awkward, therefore it has to be calculated with low concentration of emission in that substance group without doing some specific extra lowering process. That has been evaluated in numerous and voluminous test series with Alternative Fuel. The emission concentration of PCDD/F are not affected between 0,003 and 0,006 ngTE/Nm and in this case significantly lower than the limit of 0,1 ng TE/Nm. Due to exact analysis, analog assertions can be done also for polychloride Biphenyle (PCB), Polycicle aromatic hydrocarbon (PAH) and some others. Therewith the numerous doubt is disproved that substitution of regular fuel by Alternative Fuel in primary use, especially organic emission compounds, leads to significant overrun of limits.
PMT-Zyklontechnik GmbH
23
Alternative fuel
prepared domestic waste oil waste - MTA 13 8.400 2 3,3 1,23 7,6 0,15 378
0,15 35
0,4 10 to 200
124
3.000
As shown in the chart above, the major impurities are mainly consisting of Heavy Metal and Chlorine. The influence in clinker production due to that major impurities is shown as follows:
PMT-Zyklontechnik GmbH
24
Alternative fuel
Contents of Oxide and phases in clinker do not show substantial change as shown in the chart.
40% fuels substitution through thermical fraction from waste Influences on the clinker
Content on oxides and phases in [mass-%] Content on oxides and phases in [mass-%]
without plastic
70 60 50 [mass %] 40 30 20 10 0 SiO2 Al2O3 Fe2O3 CaO MgO C3S C2S C3A
5,11 21,81 21,85 17,91 66,25 66,42 59,1556,24
with plastic
20,25
8,78 9,6 8,54 8,83
5,47
2,81 2,91 1,67 1,82
1,6 1,75
C4AF
CaOfree
PMT-Zyklontechnik GmbH
25
Alternative fuel
Closing this file we conclude that the use of Alternative Fuel will give no lack in clinker mineralogy, but as known, up to now there are no affluent field test results.