The Use of Oxygen in Biomass and Waste-To-Energy Plants PDF

Venice 2010, Third International Symposium on Energy from Biomass and Waste
THE USE OF OXYGEN IN BIOMASS AND WASTE-TO-ENERGY PLANTS: A FLEXIBLE AND EFFECTIVE TOOL FOR EMISSION AND PROCESS CONTROL
N. CORNA*, G. BERTULESSI* * SIAD S.p.A., Application Development Department, Bergamo, Italy
SUMMARY: Operators of waste thermal treatment and biomass-to-energy plants can achieve lower pollutant emissions and increase capacity through the use of oxygen combustion technologies. The proper selection of the oxygen injection strategy can improve unit operation, reduce CO puff frequency and magnitude, increase throughput and allow a wider range of materials to be treated. The decision to implement oxygen-enhanced technologies, especially in the upgrading of existing plants, has to be made on a case-by-case basis, taking into consideration actual operational needs, bottlenecks and available feeds. 1. INTRODUCTION
Environmental performances of biomass-to-energy plants and waste thermal treatment systems is a hot and crucial issue that is gaining more and more importance both on technical and public acceptance side. Operators of such facilities must face, from one side, strict limitations to gaseous pollutants emission and from the other the variability of the incoming material: the supply of high and constant quality feed is in fact a serious issue for both process stability and emission control. The use of state-of-the-art oxygen combustion technologies gives the operators an effective and flexible tool able to manage most of these process problems. This paper briefly illustrates the theoretical basis of the use of oxygen in the thermal treatment of biomass and wastes and presents different configurations tested and actually working at SIADs customers. The theoretical part will focus on the after-burning or post-combustion stage and on CO and soot formation and removal. The second part will be focused on diverse upgrading options based on system properties and issues and shows the retrofits implemented in existing thermal treatment plants through the use of oxygen. The interested plants include a conventional grate system for solid fuels with underfire air and post-combustion chamber, one hazardous solid incinerator with vertical post-combustion unit equipped with liquid waste streams injection and rotary kilns for sludge pyrolysis. The applications range from oxygen use in primary combustion air, to ensure maximum flexibility to the process and lower residual carbon in the ashes, to O2 injection in secondary air, aiming to achieve high level of gaseous pollutants removal. The use of pure oxygen lancing in
Proceedings Venice 2010, Third International Symposium on Energy from Biomass and Waste Venice, Italy; 8-11 November 2010 2010 by CISA, Environmental Sanitary Engineering Centre, Italy
different configurations and the use of oxy-fuel burners are also shown. Theoretical dissertation and case samples discussion highlight the potential benefits in the use of oxygen technologies in biomass/waste-to-energy plants, but also stress the importance of case-by-case analysis since different plant configurations, operational needs, heat loads and fluid dynamic conditions require specific approaches and customized solutions. 1. EFFECTS OF OXYGEN ENRICHMENT ON GENERAL COMBUSTION CHARACTERISTICS
Oxygen enrichment of air reduces the amount of nitrogen present as diluent in the reaction of fuel and oxygen. The rate of combustion reaction usually increases significantly with oxygen enrichment due to the higher partial pressures of both oxygen and fuel and the resulting enhanced equilibrium temperature. This faster reaction rate contributes to most of the following changes in the combustion characteristics: higher flame speed; lower ignition temperature; wider flammability range; higher blow-off velocity gradients; higher adiabatic flame temperature. For incineration applications it is necessary to evaluate how these changes affect flame stability and flame temperatures.
Figure 1. Flame temperature in relation to oxygen percentage in the combustion atmosphere
Flame stability In general, a higher flame speed will improve flame stability and create a more intense and short flame. It is however difficult to predict the actual effect on systems processing biomass and wastes since flames are post mixed with various degree of turbulence. The lower flammability limit (lean limit) of a fuel and air mixture is little influenced by the O2 enrichment of air. Excess oxygen in the lean limit is considered to act as a heat sink similar to nitrogen. The upper flammability limit (rich limit), on the other hand, is extended substantially with oxygen enrichment, as shown in Table 1. Wider flammability limits generally correlate with greater flame stability (e.g. critical velocity limits for blow-off conditions). The change in the upper limit allows the combustion of fuel or waste to begin even in a highly fuel-rich mixture. Lower values of minimum ingnition energies and temperatures in pure oxygen also contribute to enhance flame stability. Table 1. Ignition and flammability properties of some combustible species in air and oxygen at atmospheric pressure (adapted from NFPA, 1984) Min. Ignition Temperature Air Oxygen (C) (C) 609 500 537 515 288 560 476 651 588 400 506 278 470 Min. Ignition Energy Air Oxygen mJ mJ 0.017 0.30 0.25 0.25 0.22 2.37 > 1000 0.0012 0.003 0.002 0.009 0.011 Flammability Limits Vol. % Air Oxygen LFL UFL LFL UFL 12.5 74 12.5 94 4.0 75 4.0 95 5.0 15 5.1 61 3.0 12.4 3.0 66 1.8 8.4 1.8 49 1.3 7.9 1.3 30 6.2 16 4.0 67.5 15.0 28 15.0 79
Combustible
Carbon Monoxide Hydrogen Methane Ethane n-Buthane Benzene Ethylene Chloride Ammonia
Adiabatic Flame temperature Adiabatic flame temperature increases significantly with oxygen enrichment due to reduction of nitrogen which acts as a diluent in combustion. The flame temperature increases by as much as 50 C for a 1% increase in oxygen concentration for low enrichment levels (see Figure 1). It is important to recognize that the adiabatic flame temperature simply provides an upper limit in the attainable flame temperature. A number of different oxygen usage techniques have been developed in the industry in order to improve the stability, efficiency and control of the combustion process in waste and biomass burning furnaces without creating higher flame temperatures that might cause local overheating problems. The use of high velocity oxygen jets, for example, allows to keep low flame temperatures because aspirated combustion gases serve as a flame heat sink (see Figure 2). Even when using oxygen enrichment of primary underfire air, the higher quantity of heat available due to the removal of part of the nitrogen from the system, can be absorbed by other sinks as, for example,
waste with higher humidity content. The correct use of oxygen will not therefore increment the combustion zone temperature, so that the grate will not exposed to overheating. It must be underlined that also in furnaces with temperature limitations and already existing localized overheated zones, the use of oxygen can be addressed to achieve better temperature uniformity within the furnaces without increasing heat release to those zones already severely loaded.
2750 Flame Temperature C

FURNACE GAS Furnace gas = 2400 F TEMPERATURE
R=O
temperature 1315C
2475
R=1 R=2
Traditional oxy-fuel burners use high flame temperature for welding and melting. SIAD advanced oxyfuel burners reduce flame temperature and reduce NOx emissions in industrial furnaces.
2200
R=4
1925
R=6 R=8
1650
Flame Temp of Natural Gas/air mixture R=Flue gas recirculation ratio
20 40 60 80 Volume% of O2 in Oxidant
100
Figure 2. Calculated reduction of adiabatic flame temperature of natural gas flame by recirculation of flue gas
2.
BENEFITS OF OXYGEN COMBUSTION
Once briefly mentioned the effects of pure O2 in a combustion process, it will be easier to understand the main advantages of its use in thermal treatment of waste and biomass. Increase in treatment capacity of the plant. Reduction in furnace emissions. Smaller flue gas handling equipment needed. Higher flexibility in the plant management and in the feed quality and composition. Reduced fuel consumption in case of low calorific fuels. Improved process stability and control. Since the erection of green field waste treatment facilities in EU is extremely rare due to environmental concerns and public acceptance, high investment costs and complex authorizations needed, the possibility for an increase in the capacity of an existing plant without major process modifications and significant investment costs is a topic of growing interest. Oxygen combustion technologies have been successfully used for increase in capacity and productivity in a broad range of industrial furnaces. While the enhanced heat transfer mechanisms typical of oxygen combustion are of little importance for waste treatment furnaces, this type of plants can benefit from the reduced specific flue gas volumes so that the throughput can be significantly increased. The extent of improvements possible for a particular incinerator
depends on the nature of the plant limitations, the most common of which are usually related to the air blower capacity, the gas residence time and the size of the flue gas cleaning system. Oxygen enhanced combustion is very effective in overcoming these limits due to the reduction of the volume of oxidant and flue gas for the same fuel input to the furnace. As can be noticed from Figure 3, in methane combustion a 3% oxygen enrichment of the combustion air results in a 12% reduction of the flue gas volume. This reduction can result in significant savings also in downsizing the air pollution control devices. The dust carryover problem another common process limitation, is related to particle size, characteristic of particulate matter and fluid dynamics within the furnace. Although the improvement due to oxygen usage varies according to the injection strategy applied, the lower superficial gas velocity due to reduced volumes inside the furnace is beneficial in reducing the dust carryover. According to Stenburg et al. (1966), the particulate emission for solid waste burning systems is essentially dependent on underfire air rate. In particular they report the release rate to be directly proportional to u0.543, where u = underfire air velocity. According to the previous empirical relation, a 3% enrichment of underfire air would result in a 7% less particulate emission.
Flue gases from CH4 combustion

The effect of O2 enrichment
100% 90% Flue Gas Vol. 80% Volume Fraction in Flue Gas 70% 60% 50% 40% 30% 20% 10% O2 0% 20% 40% 60% O2 in the oxidizer N2 CO2 H2O
12 11 10 9 8 7 6 5 4 3 2 100% Flue Gas Volume [Nm 3FLUE / Nm 3CH4 ]
80%
Figure 3. Effect of O2 enrichment on flue gas volume and composition (combustion of CH4, air/fuel ratio = 11.5, O2/fuel ratio = 2.0) Where the main limitation of the plant is the heat exchange capacity of the steam production section, a detailed study must be undertaken in order to ensure that no overheating can occur in the system, while, if the bottleneck is the solid handling capacity of the pretreatment and feeding section, mechanical modifications must be made before oxygen usage can be useful.
When an increase in throughput is not requested, the use of oxygen can be useful in order to lower pollutants emissions as well as to achieve higher treatment flexibility, especially in terms of feed quality, humidity and LHV. It is in fact not uncommon that Biomass-To-Energy plants, originally designed to treat substances with defined and specific chemical composition, need, after some years, to deal with different feedstocks because of biomass availability, cost opportunities or authorizations. Similar problems must be faced by waste thermal treatment facilities, where the properties of incoming waste is variable and the pressure exerted by public opinion is much stronger. These unpredictable variations in fuel composition together with the intrinsic complexity of the process often result in sudden variations of the conditions inside the reaction chamber and in the formation of a wide range of pollutants. Due to the possibility to remove diluent nitrogen, locally increase temperatures and lower flue gas volumes, the use of oxygen can be a very effective tool to overcome this type of operational problems. Another major issue is the variability of the water content of the feed due to seasonal variations, weather conditions, collection methods and storage facilities available. An increase in the feed humidity will necessary result in a decrease of plant capacity, waste residence time and furnace temperatures with a consequent increase of residual carbon in ashes. The use of oxygen enrichment of underfire air allows better ash burnout since less heat is carried away by the reduced volume of combustion gases and more energy is released to the load. This additional heat release improves the burning process by shortening the area needed for material drying and improving the combustion process. Oxygen can be used only when considered necessary: regardless the type of installation required (enrichment of primary or secondary air, lancing, oxy-fuel burners, etc.) the oxygen control and distribution system allows operators to choose between fully automatic, variable rates injection strategies based on external inputs, as for example the real-time flue gas analysis, to simpler manual controlled systems that can be started and stopped directly by the operator on the actual need. After a detailed study of the furnace temperatures and fluid dynamics and of the current operating conditions, the correct and customized oxygen injection technology can dramatically increase the waste blend flexibility and improve the performance of the plant due to enhanced fame stability and longer residence times as well as higher control of process temperature and excess oxygen. 3. POLLUTANT CONTROL
Organic products of incomplete combustion Waste thermal treatment is a really complex process and incinerators are not ideal combustors. Variations in the feed input, temperature perturbations, gases preferential paths, solid waste stratification and different volatilization temperatures and rates, often result in local zones of deficient oxygen where decomposition of the organic constituents proceeds through pyrolytic processes and a number of organic volatile compounds are originated. If these pyrolysis products do not undergo through adequate post-combustion residence times, temperatures, turbulent mixing and sufficient oxygen supply, some organic combustible micropollutants will escape from the system and be emitted in the atmosphere. As previously illustrated, the use of oxygen enhanced combustion can effectively overcome all the mentioned limitations, increasing residence time with the reduction of the flue gas
volumes, raising temperatures in colder furnace zones and promoting more efficient mixing between oxidant and combustible particles through localized injection strategies and higher partial O2 pressures. Carbon Monoxide (CO) Carbon Monoxide is the major compound formed during the pyrolysis and gasification phases through which biomass and waste undergo in a thermal treatment process. When, downside the CO formation, the turbulence is not sufficient, temperatures are not high enough or oxygen is not available in adequate quantities, significant CO emissions will be measured at the stack. Local non homogenous composition or unwanted stratification of the charge and variable composition of the material, can also lead to instantaneous and isolated CO emissions (puffs). In order to ensure the more complete as possible removal of CO from flue gases, the kinetic of CO oxidation must be quickly reviewed. The kinetic of CO reaction to CO2 (Hottel, 1965; Morgan, 1967; Dekker, 2002) is generally given by:
df CO b A B C P = a exp f O 2 f CO f H 2O dt RT RT Where fCO, fO2, fH2O = molar fraction of carbon monoxide, oxygen and water vapor t = time T = temperature P = pressure R = ideal gas constant t = time A, B, C, D, a, b = constants varying according to the different formulations While authors agree on B = 1 and C = 0.5, values of A range between 0.3 and 0.5. It can be noticed that the process is strongly dependent on temperature and, to a lesser extent, on partial pressure of oxygen and water vapor. Oxygen enrichment of secondary or tertiary air or pure oxygen injection through lances will have the consequence of increasing all these three parameters governing the CO oxidation rate. The reduction of the total volume will also allows higher residence times, with consequently higher removal rates. We can consider, as an example of a mixture with high CO content, the gas composition resulting from the pyrolysis of dried sludge from one of the case samples illustrated in the following section (see Table 2). To evaluate the effect of oxygen usage on CO oxidation kinetics, the rate constant, in presence of three different streams of oxidant, i.e. air, 3% oxygen enriched air and pure oxygen can be calculated based on the above model. If we consider the same temperature for the three mixtures between the combustible gas and the oxidant, the reaction rate of CO oxidation when 3% oxygen enriched air is used is between 12.0% and 12.5% higher with respect to air. In case of pure oxygen, the CO conversion for the mixture is from 8.6 to 10.8 times faster than in presence of air.
D
Table 2. Example of gas mixture with high CO content

Species Gas composition mole H2 CH4 C2H6 C2H4 C3H6 CO CO2 H2O 26.95 % 24.79 % 2.76 % 4.59 % 0.96 % 30.46 % 7.66 % 1.82 % mass 2.82 % 24.79 % 4.31 % 6.68 % 2.10 % 30.46 % 7.66 % 1.70 %
Soot
A number of approaches have been developed for soot burnout modeling and different formulations have been proposed in literature, with increasing detail level and different scope of application. Since an in depth description of the process is beyond the scope of this work, we will briefly present the base of a widely accepted approach and show the effect that the correct and aware use of oxygen can have on the removal of soot particles that can be formed in poor combustion zones of the furnace. The soot particles burnout process, as a first approximation, can be modeled studying the kinetics of heterogeneous combustion of small char particles in air and oxygen. In a carbon-oxygen system, the rate of weight loss of carbon per unit external surface area Rt is given by the so called resistance equation:
1 1 1 1 = + Rt PO 2 K s K d 1 0.75 K s = C (T ) d E K d = A exp RT
Where
Rt = rate of carbon consumption
cm 2 s K s = surface reaction rate coefficient g 2 cm s atm K d = diffusion coefficient g 2 cm s atm
0.01 0.001 R t [g / cm s] 0.0001 0.00001 0.000001 0.0000001 800 900 1000 1100 1200 1300 1400 1500 T [K]
2
Figure 4. Rate of carbon consumption for a small char particle as a function of temperature Ks represents the influence of chemical kinetics on the overall reaction rate, while Kd symbolizes the limitation to the process due to diffusion resistance. When Ks << Kd it means that the soot burnout is limited by the kinetics of the surface reaction, while with Ks >> Kd the process is constrained by the oxygen transfer rate from the boundary layer to the surface where the reaction is almost immediate. The relative importance of reaction kinetics vs. oxygen diffusion in soot burnout depends on soot particle diameter and operating temperature (see Figure 5).
100000 10000 1000 Ks , Kt 100 10 1 0.1 0.01 0.001 0.001
Ks Kt
0.01
0.1
10
100
1000
Soot particle diameter ( m)
Figure 5. Kinetic and diffusion coefficient as a function of soot particle diameter For diameters typical of soot particles the process is by far constrained by the surface chemistry, while the burnout of residual particles generated from the combustion of liquid wastes made up of long-chain organic molecules is kinetically quite different from soot burnout, mainly because the residual particles are orders of magnitude larger than soot and the rate is controlled by boundary layer diffusion. As can be noticed from the above formulations, the rate of soot burnout, in a temperature
range representative of incineration processes, can be expressed by the Arrhenius equation; the reaction is therefore strongly influenced by reaction temperature and proportional to O2 partial pressure. When trying to face issues related to soot emissions, the first actions to be taken should be addressed to improve the combustion process itself: soot emission, being generally a result of poor combustion, is in fact often associated to other uncombusted pollutants emission (CO, VOCs, dioxins, etc.). When no further improvements can be done in tuning waste or biomass burning process, the solution is to improve the soot burnout process. The use of pure oxygen injection in the colder zones of the furnace will raise the temperature of the area preventing the flue gas cooling, increase the O2 partial pressure and promote good mixing between soot particles and oxygen, thus dramatically decreasing the time required for the complete oxidation.
4.
RECENT APPLICATION OF PURE OXYGEN IN WASTE THERMAL PLANTS
Case History 1
Case sample 1 is related to the upgrade of a municipal waste incinerator in Northern Italy. The plant comprises two continuous fed lines, having moving grates, with a nominal treatment capacity of 100 t/day each. The combustion chambers consist of four mechanical grate sections providing continuous variable speed movement through oleodynamic actuator. The waste supply takes place through refuse charging hoppers terminating in vertical throats that act also as plugs for waste gases. The incineration capacity is regulated through the combustion air and the pusher movement. Underfire air is supplied through four plenums from an air duct. Combustion gases flow countercurrent to the waste feed and are conveyed to the post-combustion chamber where secondary air is injected; the chamber is equipped with auxiliary natural gas burners which automatically start whenever the temperature falls down minimum value, according the EU codes. Gases from post combustion chamber pass through a steam boiler producing high pressure superheated steam for electric energy generation and low pressure steam used for district heating. The plant, originally designed to treat MSW having different composition and source with respect to the actual plant feed, was suffering two major operational problems. The first was related to the quality of the incoming waste, which, due to the collection and storage procedures, could have high and extremely variable water content. It resulted in the worsening of burning conditions inside the chambers, with an increase of the grate fraction where drying and preheating phase took place and a consequent reduction of gasification and combustion zones. As a result, high residual carbon values were frequently found in the ashes. Increases of underfire air to solve this problem was not possible, since blowers were at full capacity and the higher volumes of primary air would have resulted in smaller residence times in the post-combustion chamber, with an increase in pollutants emission and higher loads to the waste gas treatment unit. The second issue was related sudden and unpredictable CO puffs releases. The operators, in the attempt to maintain the desired treating capacity with a feed at low LHV and high humidity, had to face a less complete combustion in the primary chamber so that the post-combustion section became overloaded with puff emissions high in carbon monoxide. The objective of our activity has been therefore to increase, from one side, the actual plant treatment capacity and
remove, from the other, CO puffs. After a detailed analysis of the operating parameters in the combustion and post-combustion chambers, a proposal based on two solutions was defined and finally applied. The primary activity was to improve the underfire air system through oxygen enrichment. The higher humidity of the waste would have required a longer grate in order to achieve a complete char burnout from the ashes since the drying zone was too wide and the gasification and combustion zones resulted insufficient. The most effective solution has been the oxygen enrichment of combustion air, creating the same effect of a longer gasification and combustion section, allowing a more intense and reactive reaction. In order to optimize the pure oxygen usage, it is sometimes useful to enrich only the portion of underfire air that is really participating in combustion, avoiding the enrichment of the air delivered to the first portion of the grate which is mostly used for drying the incoming material. In this case, since the four air distribution sections are fed through the same air duct without the possibility of independent regulation and because the grate surface is relatively limited, the enrichment has been done on all the combustion air. A simple oxygen distributing pipe, or sparger (see Figure 6), was therefore placed in the main air duct.
Figure 6. CFD simulation of Oxygen mixing through a sparger in combustion air duct An additional improvement was obtained through the positioning of oxygen lances in the postcombustion chamber. The air enrichment at the grate level has been designed at low levels (2.0%) so that the residual carbon could be decreased at the desired content without any concern for the grate integrity. To eliminate CO puffs, the injection of pure oxygen jets, just at postcombustion chamber inlet, was a very effective solution. One high velocity oxygen lance has been therefore placed concentrically inside each secondary air distribution pipe (see Figure 7) so that a turbulent mixing region with elevated oxygen partial pressure is created at the inlet of the post-combustion chamber. Since CO emission puffs in waste combustion units occur as sudden releases from the
combustion process, it is not straightforward to design a system that, in order to minimize operating costs, will intervene only when necessary. An O2 injection strategy starting only when stack CO emissions will overcome a defined threshold is likely to be both inefficient and ineffective. The analysis of the available data carried out in conjunction with the plant technicians and operators, together with the prescriptions from local authorities, made possible to identify the free O2 level at the post combustion chamber exit as the best parameter to be monitored in order to prevent CO releases. An automatic system based on the input of an oxygen analyzer placed downstream the post-combustion chamber was therefore chosen for the control of the secondary air oxygen injection, while the primary undergrate combustion air enrichment control was left at operators decision, enabling them to determine, mainly through the evaluation of the incoming material, the optimal oxygen usage. After an initial test phase where the main process parameters have been fine tuned, the results clearly indicated the full achievement of the intervention targets and the installation has been permanently implemented allowing an increment in treatment capacity of 10% 20% together with the almost complete removal of CO emission limits overcoming.
re u P
n ge y ox
la
es c n
Secondary air distribution pipe

Figure 7. Pure O2 injection lances placement in secondary air distribution system
Case History 2
The following example presents the upgrading of a thermal treatment plant based on pyrolysis/gasification in different stages in rotary kilns. The purpose of the plant is the thermal treatment of sludges and the production of inert material to be used for aggregates production for the construction industry. The plant was designed to treat about 15 t/hour of sludge at 25% dry solid content and was composed of the following main processes: sludge drying, 2-stage pyrolysis, sintering, off-gases
post-combustion and flue gases cleaning and steam production. Sludge is fed to a two-stage drier to increase the dry solid content up to 90%. In the original configuration the dried sludge was supplied into 2 pyrolysis reactors, working in parallel, indirectly heated by hot gases generated downstream in the process. From the reactors the resulting material entered into the second pyrolysis/gasification stage. The process was carried out in a rotary kiln, directly heated by combustion gases generated in a separate gas generator. The process unit, at the time of the intervention, was suffering some operational problems especially related to the two indirect heated medium-temperature pyrolysis reactors. A successful application of oxygen made possible to overcome the limits of the process and simplify significantly the plant configuration. In order to overcome the limitations of the two indirect pyrolysis reactors, where limited intervention was possible, it was proposed the customer to bypass them, providing all the energy needed for pyrolysis in a rotary kiln. The kiln has been equipped with an oxy-fuel burner specifically designed for processing fine materials. The burner has been placed at the kiln material inlet, firing co-current the material path. In this way it was possible both to capitalize the existing configuration with flue gas extraction at kiln inlet and to maximize the efficiency of the energy transfer process thanks to a longer gas path inside the furnace promoted by the U-shape flame typical of this design. The burner has a firing rate of 3 MW, allowing the maximum achievable heat transfer to the material bed; the balance between natural gas and oxygen supplied to the burner is kept at the stoichiometric value, so that the atmosphere inside the furnace is maintained neutral and non-oxidizing. The use of an oxy-fuel burner consents also to extract a pyrolysis gas with a considerable higher LHV than the one achievable with air-fuel flue gases. The gases pass through the existing cyclone and are directly fed to the post-combustion chamber. Thanks to the high achieved discharge temperature of the material, about 600 700 C, it has been possible to reach, within one single short rotary kiln, almost the complete volatilization of the organics present in the dried sludge; the residual carbon content from this stage lies between 7% and 15%. A second rotary kiln, 6 m long, equipped with two oxygen natural gas burners and an oxygen lance is used to remove the residual carbon and sinter the final product. The material discharged from the first kiln, due to the existing conveying system configuration, experience a sensible temperature loss before being charged to the second kiln so that the charge temperature falls down to values close to 400 C. The purpose of the second kiln, operating at about 950 C, is to lower under 3% the residual carbon content and perform a partial sintering of the material so that it can be easily used, after mixing with other additives, as inert in the construction industry. Since the material temperature at kiln inlet is about 400 C, it is necessary to provide a definite amount of energy just in the first part of the 6 m kiln to raise the temperatures, while at about 800 C, when the carbon burning is fast, it is crucial the availability of free oxygen to complete the combustion reaction. The choice has therefore been the installation of two high impulse oxy-fuel burners at the kiln inlet, 500 and 300 kW, providing a very short and intense flame (see Figure 8). At the same time, an oxygen injection lance, placed closed to the charge, generates an atmosphere with a high O2 partial pressure able to burn the residual carbon to the required level. Kiln inlet presents also an open section, 300 mm diameter, which promotes a determined air input ensuring enough turbulence level inside the kiln. The discharged material from the second rotary kiln is rapidly quenched in water in order to
fix the heavy metals impeding re-oxidizing conditions. The successful application of oxygen in the different sections of the plant allows today a more steady operation with higher control on process variables and a more efficient energy and plant utilization.
Figure 8. Short and intense flame of the high-impulse Oxygen-Natural Gas burner
Case History 3
Case history 3 illustrates the application of oxygen to an incinerator of industrial toxic and dangerous waste both in solid and liquid form. The incineration unit is located inside a chemical factory; the plant has the authorization to burn hazardous waste both in-house generated and on behalf of third parties. Solid waste is burnt in two static batch furnaces where primary air is supplied under the fixed grate and no secondary air injection is used. Combustion gases from the two static furnaces go to a vertical, top fired post-combustion chamber; the burner, located in the upper part of the unit, is designed to burn high-calorific liquid wastes. Secondary air is and combustion gases from the two solid waste furnaces are injected separately about 1 m below the liquid waste burner. The system was designed to treat approximately 500 kg/h of solids and 150 kg/h of liquid waste. Solid waste consists mainly of paperboard boxes, packaging, pharmaceutical and color industry waste, while injected liquids are generally spent oils and solvents. The main problem that the operators of the unit were facing was related to the worsening of the combustion conditions inside the vertical post-combustion chamber after each charging of the two solid waste furnaces. Once the batch charge was introduced, the resulting combustion gases, at relatively low temperature, immediately reached the post-combustion chamber causing a drop in temperatures and free O2; as a consequence the CO content measured in the resulting gases showed a rapid increase. To simultaneously reduce the volume of gases to the post-combustion chamber and increase their temperature, pure oxygen lancing in the two batch furnaces has been applied. One lance has been placed inside the charging door of each furnace, injecting oxygen close to the material bed. Once the batch has been charged, oxygen lancing starts and primary air is substantially lowered. This allows, from one side, an important reduction of the volume and an increase of the
temperature of the off-gases to the post-combustion chamber and from the other a faster combustion reaction process that consents to shorten the cycle. Oxygen consumption was optimized using oxygen only during the first phase of the solid incineration process, when the temperature of the combustion gases was lower. Interrupting oxygen flow before the end of the combustion phase consented also to avoid reaching higher temperatures of the charge, without the need to increase the time needed for the cooling phase. Comparison between operating data with and without oxygen clearly shows the almost complete stabilization of CO emissions within the required limits and the shortening of the solid waste combustion cycle, increasing the treating capacity of the plant. A second improvement has been realized to make possible to burn, inside the existing plant, very low calorific liquid waste without decreasing the treating capacity for solids and high LHV liquids. In addition to the mentioned wastes in fact, the customer had the need to treat about 80 kg/h of highly polluted water. As an alternative to the realization of a new and dedicated waste water treatment plant, it was proposed to burn the contaminated water inside the existing incinerator through the use of pure oxygen. This would have required, in absence of oxygen use, additional fuel input and resulted in higher volume of flue gases inside the post-combustion chamber, reducing residence times. Contaminated water injection would also have caused a cooling effect on the flame, with detrimental effect on the volatilization rate and complete combustion of both the main fuel (i.e. oils and solvents) and the contaminants in waste waters. It was therefore decided to inject waste waters through a lance, placed close to the burner and slightly inclined towards the flame; pure oxygen (about 40 Nm3/h) was chosen as atomizing fluid inside the new lance (see Figure 9). In this way the cooling effect on the flame was avoided, since the additional heat sink represented by the waters was balanced by the higher oxygen concentration. Water vaporization and complete burn off of the contaminants was promoted by the enhanced flame intensity, combustion air was reduced together with the total amount of combustion gases without affecting the free oxygen level. Maintaining the same flame temperature as before oxygen injection prevented also any increase in NOx emission.
Figure 9. Post combustion chamber with liquid waste injection
The possibility to use oxygen gave also the system the flexibility to be operated at different loads of solid wastes, oils and waste waters. If an increase in the solid treatment capacity is needed, the oxygen lancing through the charging door can be increased, while higher injection of both waste waters and oils can be achieved varying the amount of oxygen in the post-combustion chamber.
5.
CONCLUSIONS
A number of field installations have demonstrated the significant advantages of oxygen usage in the field of waste thermal treatment and biomass combustion. Common difficulties sometimes associated with conventional oxygen combustion, such as local overheating and high NOx emissions, are no cause for concern when the correct oxygen technology is applied. CO puff frequency and magnitude can be reduced, and residual values of carbon in the ashes can be decreased to the required level. Oxygen combustion technology can improve the operation and increase the capacity of the plant; materials with lower quality can also be treated without negatively affecting the process parameters. While the general principles discussed would apply to most situations, the best method to employ oxygen will vary on case-by-case basis: a detailed analysis of the process parameters and economics is therefore needed before the selection of the appropriate technology.
REFERENCES
Hottel, H. C., Williams, G. C., Nerheim, N. M., and Schneider, G. (1965). Combustion of Carbon Monoxide and Propane. 10th International Symposium on Combustion, Combustion Institute, Pittsburgh, PA, pp. 111121. McGowan, T.F. (1988). The use oxygen in industrial incinerators. Proceedings of the International Conference on Incineration of hazardous, Radioactive and Mixed Wastes by the University of California at Irvine, San Francisco, California. Min-Da Ho (1993). Recent advances in oxygen combustion technology for hazardous waste incineration. 3rd International Conference on Waste Management in the Chemical and Petrochemical Industries. Morgan, A. C. (1967). Combustion of Methane in a Jet Mixed Reactor, D.Sci. thesis, M.I.T., Cambridge, Massachusetts. Murzyn P. J., Min-Da Ho, Romano L. (1992). Oxygen enhanced hazardous waste incineration: a detailed discussion of the technology and economics. Thermal Treatment and Air Pollution Control, ppb 416-418. Niessen W. R. (2003). Combustion and Incineration Processes. Third Edition, Marcel Dekker Inc. Stenburg, R. L., Horsley, R. R., Herrick, R. A., Rose, A. H. Jr. (1966). Effects of Design and Fuel Moisture on Incinerator Effluents. JAPCA, 10:114120. Zabetakis, M. G. (1976). Flammability characteristics of combustible gases and vapors. Bulletin 627, Bureau of Mines, U.S. Dept. of Interior, Washington D.C.

The Use of Oxygen in Biomass and Waste-To-Energy Plants PDF

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Venice 2010, Third International Symposium on Energy from Biomass and Waste

Figure 1. Flame temperature in relation to oxygen percentage in the combustion atmosphere

2750 Flame Temperature C

Flame Temp of Natural Gas/air mixture R=Flue gas recirculation ratio

BENEFITS OF OXYGEN COMBUSTION

Flue gases from CH4 combustion

12 11 10 9 8 7 6 5 4 3 2 100% Flue Gas Volume [Nm 3FLUE / Nm 3CH4 ]

Table 2. Example of gas mixture with high CO content

Rt = rate of carbon consumption

cm 2 s K s = surface reaction rate coefficient g 2 cm s atm K d = diffusion coefficient g 2 cm s atm

Soot particle diameter ( m)

RECENT APPLICATION OF PURE OXYGEN IN WASTE THERMAL PLANTS

Secondary air distribution pipe

Figure 9. Post combustion chamber with liquid waste injection

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