Research & Development Information

PCA R&D Serial No. 2728

Interactions Among Gaseous Pollutants from Cement Manufacture and Their Control Technologies

by Walter L. Greer

Portland Cement Association 2003 All rights reserved This information is copyright protected. PCA grants permission to electronically share this document with other professionals on the condition that no part of the file or document is changed.

KEYWORDS
Cement kilns, pyroprocess, gaseous pollutants, origins, control technologies, sulfur dioxide, SO2, nitrogen oxides, NOX, organics, hydrocarbons, carbon monoxide, CO, carbon dioxide, CO2, ammonia, NH3, dioxins, furans

ABSTRACT
This report presents a qualitative examination of the interactions of gaseous pollutants generated in portland cement kiln systems, and their existing and potential control technologies. The cement-making process is described and the sources of the pollutants of concern are identified. The synergetic and counteractive relationships of the pollutants and technologies are presented in tabular and textual format.

REFERENCE
Greer, Walter L., Interactions Among Gaseous Pollutants from Cement Manufacture and Their Control Technologies, R&D Serial No. 2728, Portland Cement Association, Skokie, Illinois, USA, 2003, 59 pages.

TABLE OF CONTENTS
Page KEYWORDS.................................................................................................................................. 2 ABSTRACT.................................................................................................................................... 2 REFERENCE.................................................................................................................................. 2 TABLE OF CONTENTS................................................................................................................ 3 INTRODUCTION .......................................................................................................................... 4 DESCRIPTION OF THE CEMENT-MAKING PROCESS .......................................................... 5 SOURCES OF GASEOUS POLLUTANTS .................................................................................. 6 Raw Materials ............................................................................................................................. 6 Fuel ............................................................................................................................................. 7 Process ........................................................................................................................................ 8 RELATIONSHIPS OF EXISTING AND POTENTIAL CONTROL TECHNOLOGIES FOR PRIMARY AIR POLLUTANTS EMITTED FROM A PORTLAND CEMENT PLANT ......... 13 Control of Sulfur Dioxide ......................................................................................................... 19 Control of Nitrogen Oxides ...................................................................................................... 27 Control of Organics................................................................................................................... 37 Control of Carbon Monoxide.................................................................................................... 42 Control of Carbon Dioxide ....................................................................................................... 45 Control of Ammonia ................................................................................................................. 48 Control of Acid Gases............................................................................................................... 49 Control of Dioxins and Furans.................................................................................................. 52 CONCLUSIONS........................................................................................................................... 55 ACKNOWLEDGEMENTS.......................................................................................................... 55 REFERENCES ............................................................................................................................. 55

Interactions Among Gaseous Pollutants from Cement Manufacture and Their Control Technologies
By Walter L. Greer* INTRODUCTION
The purpose of this white paper is to qualitatively explore the interactions of gaseous pollutants generated in portland cement kiln systems and the emission-control technologies that have been or could be applied to these systems. The individual technologies discussed in this paper are in various states of application ranging from those that are in use and well understood to those that only have hypothetical possibilities. When these technologies are applied, there may be unexpected consequences from their application, e.g., the increased generation of other pollutants of concern. To meet multiple pollution abatement objectives, there will be a tendency to simultaneously apply more than one technology to individual kiln systems, a situation that also may have unexpected outcomes. The synergetic and counteractive interaction of the selected technologies must be considered to optimize and prioritize emission control strategies for minimum overall emissions, maximum energy efficiency, and acceptable cost. Site-specific research may have to be conducted, and compromises and choices may have to be made prior to the selection of a control scheme for a particular plant. Nevertheless, the trends and basic process principles provided in this paper can be utilized in the initial evaluation of gaseous pollutant controls on cement kiln systems. The historic gaseous pollutants of concern from cement kilns are carbon monoxide (CO), the oxides of nitrogen (NOX), sulfur dioxide (SO2), and organic emissions, i.e., in the form of total hydrocarbons (THCs) and/or volatile organic compounds (VOCs).1 The emissions of carbon dioxide (CO2) are of increasing interest because of concerns about global climate change. In whole or in part, these emissions from cement kiln systems are the products of combustion and/or high-temperature processes. The principal gaseous emissions from the pyroprocessing system in a typical descending order by volume are nitrogen, CO2, water, oxygen, NOX, SO2, CO, and hydrocarbons. The volumetric composition range of these constituents is from about 73 percent to less than 10 ppm (Greer, Dougherty, and Sweeney, 2000). Emissions of acid gases (AGs), ammonia (NH3), and dioxins and furans (D/Fs) also are of current interest. This paper provides a brief description of the cement-making process, an identification of expected and potential gaseous pollutants that are contained in emissions from cement kilns, a general description of the potential sources of the pollutants of concern, and a presentation and
Senior Technical Associate, Trinity Consultants, 25055 West Valley Parkway, Suite 101, Olathe, KS, 66061 USA (913) 390-9700, www.trinityconsultants.com VOCs are organic pollutants regulated under federal New Source Review procedures and are a subset of THC emissions from cement kilns due to the exclusion of some hydrocarbons from the regulatory definition of VOCs. Generally, VOCs are of greater interest for kilns located in ozone non-attainment areas. THCs are of greater interest for kilns burning hazardous waste as supplemental fuel, and greenfield cement kilns and raw material dryers seeking to comply with 40 CFR 63, subpart LLL.
1 *

discussion of current and potential control technologies with regard to purpose, process integration, and potential interactions between them. Listed references provide more detailed discussions of many of these points. For a variety of factors, no two cement plants are alike in design or operation. Invariably, there will be one or more plants that will differ in some aspect from the generalizations presented herein. This white paper seeks to anticipate the reactions to and the benefits from application of the listed control technologies; however, site-specific events may result in interactions that are not consistent with the authors predictions and should be investigated on a case-by-case basis.

DESCRIPTION OF THE CEMENT-MAKING PROCESS

The production of portland cement is a four step process: (1) acquisition of raw materials, (2) preparation of the raw materials for pyroprocessing, (3) pyroprocessing of the raw materials to form portland cement clinker, and (4) grinding of the clinker to portland cement (Greer, Dougherty and Sweeney, 2000). Listed in order of least to most thermally efficient, the four types of pyroprocessing systems in current use in the United States are wet, long dry, preheater, and precalciner. Other than in the wet process, hot gas from the pyroprocessing system may be used to independently dry raw materials in dedicated equipment or to simultaneously dry them during grinding in the second step of the cement-making process. The latter system is known as in-line kiln/raw mill. All cement pyroprocessing systems employ countercurrent flow to achieve heat transfer from the hot combustion products to the relatively cold raw materials. The temperature profiles of the four process types are quite different but the raw materials are essentially the same, and the final product is physically and chemically similar, i.e., the hard, gray, spherical nodules of hydraulic minerals called portland cement clinker (clinker). The rotary cement kiln is common to all cement pyroprocessing systems, and it is in this device that the raw materials are converted to clinker. Regardless of the pyroprocessing system, the raw materials are heated to incipient fusion at about 1480C (2700F) by an approximately 1870C (3400F) flame in the hottest section of the rotary kiln, i.e., the burning zone. Because of their characteristic physical configurations and temperature profiles, the respective pyroprocesses can present different emission rates of some gaseous pollutants while using the same raw materials and fuels. Likewise, site-specific variability in raw materials and fuels can result in the emission of gaseous pollutants in greater or lesser amounts than normally would be expected from a given pyroprocessing system. Each of the pyroprocesses also offers different opportunities for pollution abatement because of its inherent characteristics. Listed in descending order of typical concentration, the four elements that are required for the manufacture of clinker are calcium, silicon, aluminum, and iron. These elements are extracted directly from the earths crust as ores consisting primarily of carbonates or oxides, or are derived from secondary (waste) materials also having an origin in the earths crust. Magnesium, sulfur, sodium and potassium are other elements that appear in clinker in minor concentrations. Many other elements common to the earths crust can be found in clinker in trace amounts. The predominant fuel for cement kilns in the United States is bituminous coal with natural gas, petroleum products, and selected combustible wastes providing the balance of the thermal energy required for pyroprocessing. All the raw materials and fuels used in cement manufacture contain constituents that may contribute to one or more gaseous emissions from a rotary kiln or an in-line kiln/raw mill.

Although deceptively simple in concept, cement pyroprocessing systems are the most complex continuous chemical reactors in the world. There are many sequential, concurrent, endothermic, and exothermic chemical reactions occurring in a material production process approaching a state of equilibrium. Due to the large mass of reacting materials contained in the system and the heat capacity of the refractory materials within the system, there is a significant thermal inertia that must be considered in process and environmental control strategies. Because of this complexity, the mechanisms of formation of some minor constituents of concern are not now known or well understood; therefore, they cannot be readily controlled at the present time. Conversely, the process itself fortuitously reduces some undesirable emissions. The process can be modified to enhance its inherent ability to abate, and the product and byproduct to absorb, gaseous pollutants and their precursors.

SOURCES OF GASEOUS POLLUTANTS

The sources of gaseous pollutants from a cement kiln system are the raw materials, the fuel, and the process itself.

Raw Materials
Calcareous component. The predominant constituent of the cement raw material mix is calcium carbonate in one form or another. Most often, the calcareous component is limestone but it can be marl, chalk, or marine deposits of shell or aragonite. About 75% of the raw mix must be calcium carbonate so the degree of purity of the calcareous component determines the amount that is contained in the raw material mix. Because 48% of the weight of the calcium carbonate is carbon and oxygen, the calcareous component of the raw material mix is a significant source of CO2 emissions through calcination (decarbonization). Because all sources of calcium carbonate used in cement manufacture originated in an ocean, chlorine is present as a trace element. Although the mechanisms of formation are not clearly established, this chlorine is available in the flue gas stream for the generation of hydrogen chloride (HCl) and D/Fs. Limestone also can contain sulfur in the form of sulfates, sulfides (metallic and organic), and, rarely, elemental sulfur. Generally, sulfates pass through the kiln system without transformation into SO2, but sulfides and elemental sulfur can result in the generation of SO2 through the oxidation of sulfur in kiln systems. If localized reducing conditions exist in the pyroprocessing system, sulfates can be converted to SO2. Limestone also can contain petroleum and/or kerogens that can be partially volatilized or pyrolyzed at temperatures present at the feed end of the pyroprocesses to result in organic emissions.2 These organic constituents or their nonvolatile residues can result in CO emissions when burned in an oxygen-deficient section of the pyroprocessing system. Siliceous, argillaceous, and ferriferous components. The non-calcareous components of the raw mix may be natural in origin, e.g., sand and shale, or be derived from the wastes of other industries, e.g., steel mill scale or power plant fly ash. These materials can contain
Organic matter in sedimentary rocks primarily consists of kerogens, an insoluble material. Petroleum formation results form the thermal maturation of kerogens at depth.
2

sulfates, sulfides (metallic and organic), and elemental sulfur that have the potential to generate SO2. Organic, CO, and CO2 emissions also may result from kerogens, crude petroleum, or refined petroleum products in these components of the raw mix. Laboratory work at the Portland Cement Association (PCA) has suggested that nitrogenous constituents in cement raw materials have the potential contribute to NOX emissions from cement kilns (Gartner, 1983). Because of the extensive research project that would be required, this potential contribution has not been documented or quantified in the field; however, the potential NOX emissions from raw materials can be estimated in the laboratory. These nitrogenous constituents also may contribute to emissions of NH3. These raw materials may contain chlorine in trace amounts that could contribute to the formation of HCl or the precursors of D/Fs.

Fuel
Coal and petroleum coke. Bituminous coal is the predominant fuel used by the cement industry in the United States. Coal is often supplemented (replaced) in part by petroleum coke when the economics are favorable. Bituminous coal and coal/coke blends are prepared for combustion in direct-fired and indirect-fired coal mill systems. In 2000, coal and coke contributed 84.0% of the thermal energy used in cement pyroprocessing systems (PCA, 2002). The combustion of any carbonaceous fuel results in the formation of CO2 and the potential formation of CO if oxygen deficiency and/or poor mixing of fuel and air exist at the combustion site. In addition, localized combustion conditions affecting combustion reactions may result in the formation of other organic products of incomplete combustion (PICs). However, the relatively long gas residence time at high temperature found in cement kiln systems greatly reduces the possibility of emissions of organic PICs when compared to other processes that burn carbonaceous fuel. The sulfur contained in bituminous coal is in the form of sulfates, sulfides (metallic and organic), and elemental sulfur. The sulfides and elemental sulfur are oxidized readily to SO2 during combustion of the coal. Coal also contains nitrogenous compounds that are oxidized to NOX, i.e., fuel NOX, or converted to small quantities of free NH3 during combustion. Because petroleum coke contains the impurities from its crude oil source (Green and Maloney, 1984), it may contain a significant concentration of sulfur or nitrogen that has the potential to be oxidized to SO2 or NOX. In large part, the type of pyroprocess will determine if these impurities have a major impact on the emissions of NOX and SO2 from a cement pyroprocessing system. Solid fossil fuel may contain trace amounts of chlorine that could contribute to the formation of HCl or D/Fs. Natural gas. Although no longer a common practice, a few kilns will produce clinker over extended periods of time using natural gas as the primary fuel if it is more economical to use than coal. In some cases, natural gas may be used as a supplemental fuel, e.g., to enhance the burning of excessively wet coal from a direct-fired coal mill system. Today, most natural gas is used to bring kilns to operating temperature in preparation for the firing of solid fossil fuels. In 2000, natural gas contributed only 5.9% of the thermal energy used in cement pyroprocessing systems (PCA, 2002). The combustion of natural gas results in the formation of CO2, and the potential formation of CO and other PICs.

The sulfur and nitrogen content of natural gas is insufficient to result directly in appreciable emissions of SO2 or NOX. However, due to the formation of thermal NOX resulting from high flame temperature, the emissions of NOX increase when natural gas is used in lieu of solid fossil fuels in a particular rotary kiln. Petroleum. Most of the oil now burned in cement kilns is a refined product, e.g., diesel fuel or heating oil (both known as middle distillates), that is used to bring the kiln system to operating temperature in preparation for firing solid fossil fuel. In 2000, petroleum products contributed just 1.1% of the thermal energy used in cement pyroprocessing systems (PCA, 2002). The combustion of petroleum products results in the formation of CO2, and the potential formation of CO and other organic PICs. A refined petroleum product normally contains low concentrations of sulfur and nitrogen but could make a minor contribution to the formation of SO2, NOX, or NH3. Waste. Combustible wastes of industry and consumers can be used in cement kilns to supplement traditional carbonaceous fuels. In a few cases, a waste-derived fuel has completely supplanted fossil fuel as the primary fuel for a kiln. The use of waste fuels provides a mutually beneficial outcome for the environment and the cement plant. The environment is not impacted by land disposal of the waste or non-beneficial incineration. Less fossil fuel is burned while the cement plant often is able to enjoy a more favorable fuel cost. The four most common wastes burned in cement kilns are used or rejected automobile and truck tires, blended liquid and solid hazardous wastes, used oil, and combustible nonhazardous solid wastes (PCA, 2002). In 2000, 57% of the cement plants reporting data to the PCA used some form of waste-derived fuel (PCA, 2002). In 2000, wastes contributed 9.0% of the thermal energy used in cement pyroprocessing systems (PCA, 2002). The combustion of waste-derived fuel results in the formation of CO2, and the potential formation of CO and organic PICs. These wastes may contain sulfur, nitrogen, and/or chlorine that could contribute to the formation of SO2, NOX, NH3, HCl, or D/Fs.

Process
Pyroprocess description. The formation of gaseous pollutants primarily occurs in an independent kiln system or in an in-line kiln/raw mill as the consequence of oxidation or other processes at a relatively high temperature, e.g., greater than 315C (600F). The exception is the potential formation of certain PICs and D/Fs at a lower temperature. There are a few plants at which these pollutants are generated in small quantities in an independent raw material or solid fuel dryer. A discussion of dryer emissions is beyond the scope of this white paper; however, they are quite similar to those formed in the low-temperature section of a pyroprocessing system. Process gas is vented through as many as three points in a cement pyroprocessing system. Each of these vent points, i.e., the discharge of the rotary kiln or the in-line kiln/raw mill, the alkali bypass, and the coal mill, are equipped with a particulate matter control device (PMCD). All pyroprocessing systems have a kiln or an in-line kiln/raw mill vent but not necessarily alkali bypass or coal mill vents. The PMCDs may have monovents, horizontal discharge ducts, or vertical stacks. If there is a stack for the kiln or the in-line kiln/raw mill, it is usually called the main stack. Either or both of the vents from the alkali bypass and the coal mill may be ducted

to the main stack, or they may be vented independently. The gaseous pollutants that are emitted from a particular process vent are generally dependent on the type of pyroprocessing system, the site-specific raw materials and fuel, and the events occurring in the process upstream of the vent with respect to flue gas flow. In the traditional wet and long-dry pyroprocessing systems (Figure 1), the primary fuel is burned at the hot end of the rotary kiln. Supplemental fuel, e.g., scrap tires, may be burned at mid-kiln using a system or device to introduce the fuel through the rotating kiln shell. In this situation, the amount of supplemental fuel used in the kiln is limited because combustion air required by the supplemental fuel must pass through the burning zone of the kiln and serves to cool the main flame. If cooled sufficiently, the temperature of the main flame will not support the formation of the clinker minerals and the clinkering process cannot be sustained. In preheater kiln systems (Figure 2), the primary fuel also is burned at the hot end of the rotary kiln and all combustion air passes through the burning zone. Supplemental fuel may be dropped into the feed end of the rotary kiln, introduced into the rotary kiln through the kiln shell, or injected into the riser duct between the feed end of the rotary kiln and the preheater tower. In the application of these practices for supplemental-fuel combustion, the cooling of the main flame by excess air passing through the burning zone also occurs. The most modern pyroprocessing system is the precalciner kiln system (Figure 2). In this process, there is a special vessel called a calciner located between the rotary kiln and the preheater tower into which fuel is introduced. It is in this vessel that the bulk of the calcination of the calcareous component of the raw mix takes place. The calcination reaction requires the most thermal energy of any reaction in the cement-making process. This reaction commences at about 870C (1600F) and does not require the 1870C (3400F) flame temperature found in the burning zone to be sustained. Typically, hot tertiary air is taken from the clinker cooler or kiln firing hood and ducted outside the kiln to the precalciner vessel for combustion support. In an air-through calciner design, the combustion air for the calciner must pass through the burning zone of the kiln and also results in cooling of the flame in the burning zone. In a precalciner kiln system in which tertiary air is used, approximately 60% of the fuel can be burned in intimate contact with the raw materials in the calciner to achieve approximately 90% calcination of the raw mix in just a few seconds after its introduction into the preheater tower and before it enters the rotary kiln. In a traditional rotary kiln system, calcination requires much more than an hour to complete depending on the kiln size and rotational speed. The precalciner configuration of a cement pyroprocessing system is the most fuelefficient and stable of the four types. When compared to the other pyroprocesses, this system provides the highest clinker production rate with the shortest rotary kiln and the smallest footprint on the ground. Sulfur dioxide. Sulfur dioxide results from the oxidation of sulfide or elemental sulfur contained in the fuel during combustion. In addition, sulfide or elemental sulfur contained in raw materials may be roasted or oxidized to SO2 in areas of the pyroprocessing system where sufficient oxygen is present and the material temperature is in the range of 300-600C (570-1110F) (Miller, Young, and von Seebach, 2001). In addition, sulfates in the raw mix can be converted to SO2 through localized reducing conditions in the kiln system.

Raw Material Mix to Kiln PMCD

Mixing Air Fan

Mid-kiln Firing

Fuel and Primary Air Secondary Air I.D. Fan CKD Bin Rotary Kiln Clinker Cooler Clinker Discharge

Figure 1. Wet/long-dry kiln systems.

Raw Material Mix to Preheater

Preheater

Raw Material Main PMCD

In-line Raw Mill Alkali Bypass To PMCD

Fuel Calciner Tertiary Air Duct

Fuel and Primary Air Secondary Air Rotary Kiln Clinker Cooler Clinker Discharge

To Preheater Tower I.D. Fan Raw Material Mix Silo

Figure 2. Preheater/precalciner kiln systems.

Nitrogen oxides. It has been shown that nitrogen oxide (NO) makes up 90% or more of the NOX contained in cement kiln flue gas. Nitrogen dioxide (NO2) comprises the balance of the nitrogen oxides (Penta, 1991). There are four mechanisms of NOX formation in cement kilns of which thermal and fuel NOX formation are the most important. Thermal NOX results from the oxidation of molecular nitrogen in air at high temperature. This phenomenon occurs in and around the flame in the burning zone of a cement kiln at a temperature greater than 1200C (2200F). Fuel NOX results from the oxidation of nitrogen in the fuel at any combustion temperature found in the cement process. Because of the lower combustion temperature in the calciner and some sites of supplemental fuel combustion, the formation of fuel NOX often exceeds that of thermal NOX at these locations. The generation of feed NOX has been demonstrated only in the laboratory by 10

heating nitrogen-containing cement raw materials to the range of 300-800C (570-1470F) in the presence of oxygen. Slow heating, such as occurs in wet and long-dry kilns, appears to increase the yield of NOX for a given raw material. The yield of feed NOX is potentially lower when the raw material is heated quickly in a preheater or precalciner system. Prompt NOX is generated by the reaction of certain fuel-derived radicals with elemental nitrogen in a hydrocarbon flame and is a minor contributor to overall NOX generation (Penta, 1991). Carbon monoxide. CO is a PIC of carbonaceous fuels resulting from insufficient oxygen at the combustion site, insufficient mixing of oxygen and fuel at the combustion site, and/or rapid cooling of the combustion products to below the ignition temperature of CO prior to its complete oxidation. CO can be formed unintentionally at any of the combustion sites in the pyroprocessing system. The emission of CO usually represents partially burned and under utilized fuel. However, as a result of using oxygen-deficient combustion in the riser duct or calciner as a NOX control strategy, CO sometimes is generated in the pyroprocess and may appear in the flue gas discharge if it is not somehow oxidized following its formation. Organic emissions. VOCs are organic compounds that generally contain from one to seven carbon atoms in the respective molecules and are a subset of THC emissions from cement kilns. VOC emissions from cement kilns are of interest because of their involvement in the formation of atmospheric ozone and the designation of some VOCs as hazardous air pollutants (HAPs). There is no available continuous emission monitor (CEM) to quantify VOC emissions in stack gas. However, the concentration of THC emissions in the exhaust from a cement pyroprocessing system can be measured by a CEM. As stated in the United States Environmental Protection Agency (USEPA) Test Method 25A, 1.1, a THC CEM may not measure all potential THCs; however, the measurement of THCs serves as an accepted surrogate for organic emissions from cement kilns (USEPA, 1999). For purposes of this paper, THCs also serve as a surrogate for VOCs because molecules with seven carbon atoms or less are thought to comprise more than half of the THCs in cement kiln emissions (Ash Grove, 1998). THCs are primarily generated as a result of evaporation and/or cracking of the constituents of petroleum and kerogens found in the raw material mix. The potential for organic emissions varies with the selection of raw materials and the variability of the concentration of organic constituents within raw material sources. Organic PICs also can be formed as a result of incomplete combustion at any of the combustion sites within a pyroprocessing system. Carbon dioxide. Carbon dioxide results from the combustion of carbonaceous fuel and the calcination of the calcareous component of the raw material mix, an essentially unavoidable and fixed consequence of cement manufacture. Of the total amount of CO2 emitted from a cement kiln, about half of the CO2 originates from the raw material while the other half originates from the combustion process. There is about one ton of CO2 emitted per ton of clinker produced. More thermally efficient systems emit slightly less than one ton while less thermally efficient systems emit slightly more than one ton. Ammonia. Trace quantities of NH3 in the exhaust gas from a cement kiln gas probably result from the pyrolysis of nitrogenous compounds in fossil fuels and raw materials. Ammonia emissions from cement kilns are of primary concern with regard to their potential contribution to

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regional haze. In addition, atmospheric reactions occur just outside of the stack between NH3 and the oxides of sulfur or HCl that produce ammonium sulfate, ammonium bisulfate, or ammonium chloride as very fine particulate matter (PM). These reaction products are observed as the undesirable anomaly known as a detached plume. Depending on the location of the stack observer, the detached plume can give the incorrect appearance of poorly controlled PM emissions from a kiln stack. If NH3 were used as a reagent in a NOX control technology, unreacted NH3 could result in ammonia slip that would contribute to regional haze and/or a detached plume. Technologies for cement kilns that use NH3 to control NOX emissions are the only technologies that introduce a potential gaseous air pollutant to the cement process to control another air pollutant. Acid gases. All the oxidants necessary to convert SO2 to sulfur trioxide (SO3) are present in the combustion products of fossil fuel (Miller, 2001). Therefore, emissions of SO3 and/or sulfuric acid mist are a possibility from cement plants. The emissions of sulfuric acid mist also may increase for those plants employing tailpipe wet scrubbers. The mechanism for the formation of HCl in cement kilns is not fully understood. However, emissions of HCl from cement kilns have been reported over a wide range of values. Perhaps because of the affinity of chlorine for calcium and alkali metals, there is limited evidence that HCl emissions may be independent of chlorine input to a kiln system. Should there be fluorine naturally present in the raw materials or added as a mineralizer, the emission of hydrogen fluoride (HF) from a cement kiln system is a possibility. Dioxins and furans. The USEPA has determined that D/Fs are generated in the PMCDs serving the main and alkali bypass stacks of cement kilns and in-line kilns/raw mills as a function of the temperature at the inlet of the PMCD. Although the mechanism of formation has not been fully determined, USEPA has concluded that there is sufficient empirical evidence to establish the maximum inlet temperature to the PMCDs serving the pyroprocess at 204oC (400oF) as the maximum available control technology for cement kilns (USEPA, 1999). Based on currently available data, process engineers in the cement industry generally agree that the predominant variable in the formation of D/Fs is residence time in the critical temperature window. Most often, this process state occurs in the PMCD serving a rotary kiln and/or an inline kiln/raw mill but it can occur elsewhere, e.g., in a lengthy duct.

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RELATIONSHIPS OF EXISTING AND POTENTIAL CONTROL TECHNOLOGIES FOR PRIMARY AIR POLLUTANTS EMITTED FROM A PORTLAND CEMENT PLANT
The production of portland cement clinker in simple rotary kilns was once an industrial art. Process instrumentation and controls were rudimentary. In every plant, the visual and anticipatory skills of the indispensable employee known as a kiln burner had a significant impact on the quality and quantity of clinker that was produced. The application of analog instrumentation in the middle of the twentieth century quickly introduced elements of science and engineering to the process. The first successful digital computer-controlled cement kiln in the United States was commissioned in 1969. The Clean Air Act of 1970 necessitated the installation of PMCDs on the wet and long-dry process kilns that comprised the pyroprocessing system inventory at that time. The new electrostatic precipitators (ESPs) and fabric filters required induced draft fans for proper operation. The fans and their associated adjustable dampers also provided a means to control combustion parameters as never before. Oxygen and combustible gas analyzers were the first continuous monitoring systems applied to kiln flue gas. Shortly thereafter, crude CEMs for NOX and SO2 became available and were applied to a few cement kilns. There were several interesting discoveries resulting from this instrumentation. The emissions of SO2 from the alkaline environment of a cement kiln were greater and more prevalent than previously anticipated. The relative emissions of NOX from a specific kiln were found to be an excellent indicator of changes in its burning zone temperature. The significant variability of SO2 and NOX emissions from a normally operating kiln was established. The concentration of NOX emissions in the flue gas from a particular kiln was found to be highest when burning natural gas, lowest when burning coal, and in between when burning oil. The inverse relationship of SO2 and NOX emissions was observed when excess oxygen in the kiln flue gas was varied. The last two observations were the forerunners of the interrelationships of pollution control technologies that are of interest in this white paper. Later, these two relationships would prove to be invalid when applied to precalciner kiln systems and would signal the fact that each of the cement pyroprocessing systems behaves differently with regard to emissions of pollutants. Increasing concerns about the environmental effects of smokestack industries and the environmental regulations that were promulgated to protect ambient air caused the cement industry to more carefully consider its emissions and to apply new technologies to limit those emissions. At the same time, energy shortages and the resulting price increases for fuel gave rise to new, more efficient pyroprocessing systems that often resulted in less pollution. There was early and intuitive synergy between efficiency and pollution prevention. The first preheater kiln systems in the United States were installed on long-dry kilns to cool flue gas without water sprays so that fabric filters could be used to meet PM standards. The resulting improved thermal efficiency and lower NOX emissions were an incidental and synergetic benefit. The surprising predominance of fuel NOX from a calciner caused the precalciner process to be reconsidered and modified to reduce NOX emissions. New technologies were developed and technologies from other industries were adapted to deal with other pollutants. Emerging technologies are expected to be used to further control pollutant emissions from cement kiln systems. The following tables and text present a discussion of the interaction of currently available and potential emission control technologies for cement kiln systems, and their effects on the pollutants of concern. In addition to the synergetic and counteractive effects on gaseous 13

pollutants, mention is made of the effects on PM and other relevant environmental concerns, e.g., detached plumes and waste disposal. A synergetic effect is one that would be expected to decrease the generation or emission of other pollutants and a counteractive effect is one that would be expected to degrade environmental performance or product quality. Even in the same pyroprocessing class, no two cement kilns operate exactly alike. There may be no apparent explanation for the difference in behavior even for identically appearing kiln systems operating at the same site. The following generalities about the interactions of the pollution control technologies are important to understand but there always will be site-specific exceptions. Tailpipe technologies are seldom precluded by pollution abatement technologies that are applied prior to or in the main and/or bypass PMCDs in the cement pyroprocess. More than one of the pre-PMCD technologies can be applied simultaneously to the pyroprocess to reduce the generation or emission of the same or different pollutants. Although this white paper does not attempt to evaluate the economics of any of the pollution abatement technologies, pre-PMCD technologies generally are more desirable from the standpoint of process compatibility and cost. From a practical standpoint, tailpipe technologies tend to be mutually exclusive and often have associated costs that put the economic viability of a cement pyroprocess in jeopardy. Those technologies that result in the cooling of flue gas will affect the dispersion characteristics of the flue gas plume and, if all other factors were equal, would tend to increase the ground-level concentration of residual pollutants of concern. Table 1 presents a summary of the gaseous pollutant-control technologies that are currently available for cement kilns, and their synergetic and counteractive effects. Similarly, Table 2 presents the potential control technologies for gaseous emissions from cement kilns. The existing and potential control technologies are described and discussed in succeeding sections of the white paper on a pollutant-by-pollutant basis.

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Table 1. Existing control technologies for gaseous pollutants from portland cement manufacturing Existing control technologies Inherent scrubbing Oxygen / excess air control Increase Decrease Pollutant for which technology was intended SO2 SO2, THC, CO NOX SO2 SO2 THC, CO CO2 AG SO2 SO2 SO2 SO2 SO2 SO2 SO2 SO2 SO2 AG NOX NOX NOX NOX NOX NOX NOX NOX NOX, THC, CO NOX PM SO2 CO, CO2, SO2 AG, D/F AG, D/F D/F, detached plume, waste disposal Process specific NH3, HCl SO2 CO2 Burner/application specific Application specific Project specific Project specific PM Burner/application specific Application specific Project specific Project specific CO CO Process specific AG, PM, solid waste disposal, wastewater CKD disposal CO2 Fuel specific Material specific Material specific Material specific Material specific Material specific THC, AG, NH3, D/F, detached plume D/F Potential effects Synergetic Process specific Counteractive Process specific NOX, CO2 SO2, CO, product color and quality Fuel specific Material specific Material specific Material specific Material specific Material specific THC, detached plume PM NOX, CO2

Fuel substitution (lower sulfur) Lower sulfide Raw material substitution containing Lower organics Lower carbonates Lower sulfide or chloride

Raw material alkali/sulfur balance In-line raw mill Preheater upper stage hydrated lime injection Calcined feed recirculation Cement kiln dust internal scrubber Preheater upper stage trona injection Calcium-based internal scrubber Pyroprocessing system design Tailpipe wet scrubber Decrease SO2 generation Indirect firing Low-NOX burner Mid-kiln firing Process improvements Process control improvements Low-NOX calciner Staged combustion Semi-direct firing Mixing air fan Cement kiln dust insufflation

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Table 1. Existing control technologies for gaseous pollutants from portland cement manufacturing (continued) Existing control technologies Biosolids injection Inherent process characteristics (time, temperature, and turbulence) Pyroprocessing system design Regenerative thermal oxidizer Good combustion practice Improved thermal efficiency Clinker substitution Pollutant for which technology was intended NOX THC THC, CO THC, CO CO CO2 CO2 CO Process specific Detached plume, D/F NOX, CO2, SO2, THC Project specific Reduction in all gaseous pollutants per ton of cement produced Reduction in all gaseous pollutants per ton of cement produced NOX Reduction in all pollutants related to power generation Project specific Reduction in all gaseous pollutants per ton of cement produced Reduction in all gaseous pollutants per ton of cement produced AG Reduction in all pollutants related to power generation Process specific NOX, CO2, SO3, AG, waste disposal Potential effects Synergetic Counteractive CO, NH3, detached plume, metals

Improved electrical efficiency Mineralizers Electricity generation from waste heat PMCD inlet temperature control Reduced residence time at temperature

CO2 CO2 CO2 D/F D/F

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Table 2. Potential control technologies for gaseous pollutants from portland cement manufacturing Pollutant for which technology might be intended SO2, NOX, CO, THC SO2 SO2 SO2 SO2 SO2, THC, CO NOX SO2 SO2 SO2, AG SO2 NOX CO2 NOX NH3 D/F NOX NOX NOX NOX NOX NOX NOX NOX D/F NOX PM SO2, THC, D/F SO2, AG PM Water discharges, ozone slip CO, SO2 NH3, CO2, detached plume, solid catalyst wastes Water discharges CO, CO2 SO2, CO AG THC AG, THC, D/F THC, NH3, AG, detached plume Fuel/process specific Fuel specific Material specific Material specific Material specific Fuel/process specific Fuel specific Material specific Material specific Material specific NH3, detached plume Waste disposal CO, NOX, CO2 NOX, CO, CO2, waste disposal Potential effects Synergetic Counteractive

Potential control technologies Mixing air fan In-line raw mill hydrated lime injection Fabric filter absorption Sodium-based internal scrubber Calcium/sodium based internal scrubber Oxygen enrichment Dual-alkali process (soda ash/lime) Thermal decomposition (roasting) Tailpipe dry scrubber Cement kiln dust tailpipe scrubber Fuel substitution Raw material substitution containing Low nitrogen containing fuel High hydrocarbon containing fuel Lower nitrogen Lower ammonia Lower D/F

THC, AG, D/F, detached plume AG AG, D/F, detached plume AG, D/F CKD disposal CKD disposal NOX

Selective noncatalytic reduction Modified direct firing LoTOX scrubber Flue gas recirculation Selective catalytic reduction Tri-NOX Multi-Chem wet scrubber Water/steam injection Catalytic filtration Non-thermal plasma

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Table 2. Potential control technologies for gaseous pollutants from portland cement manufacturing (continued) Pollutant for which technology might be intended THC THC, CO THC, CO THC, AG THC, D/F THC, CO THC, D/F THC, D/F CO2 NH3, AG AG AG AG NOX, SO2, metals NOX, SO2, metals Reduction in all pollutants related to power generation SO2, THC SO2 SO2, D/F, detached plume SO2, NH3, THC, D/F, detached plume Waste disposal Water/waste disposal D/F D/F SO2, NOX, PM, NH3, D/F, detached plume Potential effects Synergetic Counteractive SO2, CO CO2, NOX CO2, NOX Waste disposal, water treatment CO CO2, NOX Waste disposal, high reagent consumption D/F, waste disposal, high reagent consumption Reduction in all pollutants related to power generation PM, acid mist, wastewater

Potential control technologies Thermal desorption (roasting) Thermal oxidation Recuperative thermal oxidation Wet electrostatic precipitator Ultraviolet light Catalytic oxidization Granular activated carbon adsorption Powdered activated carbon adsorption Electricity generation from the sun and wind Tailpipe wet scrubber Fabric filter absorption Tailpipe dry bicarbonate injection Temperature control

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Control of Sulfur Dioxide

Table 3. Sulfur Dioxide Control Technologies. Control technologies Potential effects Synergetic Existing control technologies Inherent scrubbing Oxygen control (increase) Fuel substitution (lower sulfur) Raw material substitution (lower sulfide) Raw material alkali/sulfur balance In-line raw mill Preheater upper stage hydrated lime injection Calcined feed recirculation Cement kiln dust internal scrubber Preheater upper stage trona injection Calcium-based internal scrubber Pyroprocessing system design Tailpipe wet scrubber NH3, HCl Potential control technologies Mixing air fan In-line raw mill hydrated lime injection Fabric filter absorption Sodium-based internal scrubber Calcium/sodium based internal scrubber Oxygen enrichment Dual-alkali process (soda ash/lime) Thermal decomposition (roasting) Tailpipe dry scrubber Cement kiln dust tailpipe scrubber NOX, CO, THC THC, AG, D/F, detached plume AG AG, D/F, detached plume AG, D/F CO, THC AG HC AG, D/F THC, NH3, AG detached plume CKD disposal CKD disposal NOX Waste disposal CO, NOX, CO2 NOX, CO, CO2, waste disposal AG, D/F AG, D/F D/F, detached plume, waste disposal Process specific AG, PM, solid waste disposal, wastewater CKD disposal CO Fuel specific Material specific Material specific THC, AG, NH3, D/F, detached plume D/F THC, detached plume PM NOX, CO2 Process specific NOX, CO2 Counteractive

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Existing control technologies.

Inherent scrubbing. All cement pyroprocessing systems have the characteristics required to remove some SO2 from the flue gas stream. These include oxidizing atmospheres, long residence times, appropriate process temperature windows, intimate mixing of gases and reactive solids, and the ability to remove from the process an intermediate material, i.e., cement kiln dust (CKD), that contains absorbed sulfur. Without application of additional technology, the authors experience is that the least effective cement kiln system captures as much as 50% of the sulfur input to the system. Likewise, capture efficiencies for sulfur in the range of 90-95% without added technologies are not uncommon in any of the cement kiln systems. High capture efficiencies are more prevalent in precalciner kiln systems with an in-line raw mill. It is not expected that any pollution control technology mentioned herein would detrimentally affect the inherent scrubbing potential of any cement pyroprocessing system. Oxygen control (increase). For control of SO2 originating in fuel, an increase in oxygen (excess air) in the rotary kiln tends to oxidize sulfur to a solid sulfate that is retained in the clinker or expelled from the system with the CKD. Because excess air passing through the burning zone increases the oxygen concentration at the combustion site, there is usually a concurrent increase in the generation of NOX. If there are localized reducing conditions in the kiln because of flame impingement or other causes, the increase in oxygen may not reduce SO2 emissions but NOX emissions may increase. If the initial combustion conditions have resulted in CO in the flue gas, the increase in oxygen concentration may decrease or eliminate the CO. There is a small increased energy requirement to heat the excess air in the system that must be overcome by additional fuel and a resulting slight increase in CO2 emissions. Because of the inherently high removal efficiency for fuel-based SO2 in a calciner, oxygen control at this combustion site would not be expected to improve SO2 removal in precalciner systems. Fuel substitution (lower total sulfur). In precalciner kiln systems, the emission of SO2 that originates in the fuel is often nil because of the inherent ability of the calciner and an alkalibypass equipped kiln to absorb and/or remove sulfur. In the other systems and under certain process conditions, e.g., a deficiency of alkali metals, sulfur in the fuel can result in emissions of SO2. It is intuitive that a reduction in the sulfur content of a solid fuel or the change to a sulfurfree fuel, e.g., natural gas, has the potential to reduce SO2 emissions. Because of the complexities of the cement pyroprocess, a change in the sulfur content of the fuel does not always result in expected changes in SO2 emissions. Whenever a fuel is changed, there may be unintended effects on the process and the resulting pollutants. For example, the replacement of coal with natural gas in a long-dry kiln system to reduce SO2 emissions will result in an increase in NOX emissions. Because energy costs nominally represent about one-third of the cost of cement manufacture, fuel substitution at a particular plant may not be economically viable. Raw material substitution (lower sulfide sulfur). Primarily appropriate for preheater and precalciner kilns, the replacement of a raw material that contains sulfide sulfur with one of lower sulfide sulfur concentration reduces the potential for generation of SO2 in the upper stages of the preheater tower. Sulfide sulfur in cement raw materials is most often in the form of iron pyrite but other sulfide compounds, including those of organic origin, may contribute to the potential for SO2 generation. Selective purchasing, selective quarrying or judicious blending of available

20

raw materials is used to accomplish the replacement. Whenever a raw material is changed, there may be unintended effects on the process and the resulting pollutants. For example, the new raw material with a lower concentration of sulfide sulfur might result in the need for a higher temperature in the burning zone that would tend to require more fuel and cause higher NOX and CO2 emissions. Because cement plants normally are located at or near their sources of raw materials, there are often critical economic limitations to the practicability of substituting raw materials to reduce the input of sulfide sulfur. SO2 has been shown to be an inhibitor to the formation of D/Fs (Richards, 2003) Raw material alkali/sulfur balance. Another raw material substitution method that is potentially applicable to all kiln systems is to stoichiometrically balance the sulfur in the kiln system with the alkali metals, sodium and potassium. Under oxidizing conditions in the kiln, the sulfur preferentially forms alkali sulfates. If there is a deficiency in alkali metals, SO2 can pass through the system even though there is an apparent abundance of calcium oxide with which the SO2 could react and be retained in the clinker or CKD. Balancing the input of alkali metals to the input of sulfur has been shown to reduce SO2 emissions. However, alkali metals are deleterious to the performance of portland cement in some concretes and the concentration of these metals in cement is frequently limited by specification. Because of this concern for product quality, it may not be possible to introduce a sufficient quantity of alkali metals into a kiln system to stoichiometrically balance a high-sulfur input. Whenever a raw material is changed, there may be unintended effects on the process and the resulting pollutants. For example, a new, higher-alkali raw material also might contain nitrogenous compounds that potentially would contribute to increased emissions of NOX. Because cement plants are normally located at or near their sources of raw materials, there are often critical economic limitations to the practicability of substituting raw materials to alter the alkali/sulfur balance through selective purchasing, selective quarrying or judicious blending of available raw materials. In-line raw mill. The use of hot exhaust gases from a dry kiln system to simultaneously dry the raw materials during grinding is a common practice to improve the overall thermal efficiency of a plant. In-line raw mills most often are found as components of new or reconstructed preheater and precalciner kiln systems. In-line raw mills are seldom, if ever, added to an existing dry kiln system solely as a pollution control technology. The presence of finely divided calcium carbonate in the high-moisture atmosphere of an in-line raw mill (particularly vertical roller mills), and the intimate contact of the solids and flue gas, result in an excellent SO2 scrubbing environment. Reductions in the concentration of SO2 in the flue gas are commonly in the range of 40-60% during mill operation. When the in-line raw mill is down for maintenance or raw mix inventory control, the flue gas is not treated in the mill and SO2 emissions measurably increase unless otherwise controlled. Most in-line kiln/raw mill systems are designed for the mill to be down only 8-16 hours per week while the kiln is operating. In limited, unpublished testing familiar to the author, operation of in-line raw mills also have been shown to reduce the emissions of THC, AG, NH3, and D/F. However, observations have been made of the release of THC emissions from the matrix of the raw material mix during grinding. Detached plumes also may be reduced or eliminated when the in-line raw mill is in operation because the plume constituents have been reduced in concentration or eliminated by the gas scrubbing action within the mill. Conversely, a release of NH3 has been observed during

21

grinding of nitrogen-bearing raw materials that caused a detached plume under favorable atmospheric conditions. Because an in-line raw mill utilizes most of the sensible heat in the flue gas, the application of tailpipe technologies requiring an elevated temperature, e.g., a dry scrubber, requires additional fossil fuel combustion (and the resulting increase in CO2 and NOX emissions) to reheat flue gas that has passed through an in-line raw mill. Preheater upper stage hydrated lime injection. To serve as an SO2 absorbing reagent, powdered hydrated lime (calcium hydroxide) can be introduced into an appropriate location in the upper stages of the preheater tower that is an integral component of both preheater or precalciner kiln systems. The hydrated lime and SO2 can react directly or, more likely, the hydrate is converted to calcium oxide at 522oC (972oF) to form an effective scrubbing reagent at the location in the process where sulfide sulfur is being converted to SO2. Probably due to variations in the point of reagent injection, mixing efficiency, and the retention time of the reagent in the required process temperature window, a wide range of scrubbing efficiencies has been observed for this technology. Due to the receipt and handling of powdered hydrated lime, there will be a small increase in PM emissions from the plant using this technology. It is possible that the concurrent removal of HCl and Cl2 from the flue gas at this point in the process will suppress the subsequent formation of D/F (Richards, 2003). Calcined feed recirculation. F.L.Smidth has developed a proprietary process, De-SOX, in which a small quantity of partially calcined kiln feed, e.g., 5%, is removed from the calciner vessel of a precalciner kiln system and pneumatically conveyed to an appropriate point in the upper stages of the preheater tower. The calcium oxide in the calcined feed is an effective scrubbing reagent at the location in the process where sulfide sulfur is being converted to SO2. Scrubbing efficiencies for SO2 of 25-30% have been reported anecdotally. This system is perhaps more convenient and cost effective than the injection of purchased hydrated lime. Because of the recirculation of material, there is a small increase in the thermal energy requirements that results in additional NOX and CO2 generation due to additional fuel consumption. Other vendors may offer similar systems. Cement kiln dust internal scrubber. F.L.Smidth has developed another proprietary process, Gas Suspended Absorption (GSA), in which dry, lime-rich CKD from the alkali bypass PMCD on a precalciner kiln system is recirculated to the conditioning tower ahead of the bypass PMCD in the gas flow path. In the presence of the water in the conditioning tower that is used for temperature moderation, this calcium oxide becomes an effective SO2 scrubbing reagent. Because of the pyroprocess is the source of the scrubbing reagent, the amount of CKD that is bled from the GSA system and subsequently wasted is not increased beyond the amount that ordinarily would be wasted from the alkali bypass. Should enhancement of the CKD scrubbing potential be required, dry hydrated lime can be added to the CKD introduced into the conditioning tower. In this situation, the amount of wasted CKD would be increased by the amount of hydrated lime added to the process. The GSA process is only applicable to the gas stream that passes through the alkali bypass and only would control SO2 originating from the fuel used in the burning zone or from sulfates locally reduced to SO2 in the rotary kiln (Vu, 2003). The emissions of AGs, e.g., HCl and Cl2 also might be reduced in quantity and concentration. The reduction of these potential precursors to D/F emissions, may serve to suppress the generation of D/F in the PMCD. Other vendors may offer similar systems.

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Preheater upper stage trona injection. A variant of the hydrated lime injection technology is the use of powdered trona, a naturally occurring crystalline form of sodium carbonate/sodium bicarbonate, as the absorbing reagent in a preheater tower. At temperatures found in the preheater tower, the sodium salt decomposes to sodium oxide with which the SO2 can react and form a relatively stable solid. Because the sodium remains in the process, care must be exercised that an increased concentration of sodium in the clinker does not render the resulting cement unmarketable. If necessary to reduce the alkali content of the clinker, alkalirich CKD could be removed as a by-product from the pyroprocess through an alkali-bypass system. This CKD would require subsequent management including the possibility of disposal in a suitable landfill. Trona is more expensive than hydrated lime but is a more efficient reagent. Manufactured sodium carbonate and/or sodium bicarbonate may be substituted for trona. To the degree that this technology also absorbs the AG precursors to D/F formation, HCl and Cl2, that are present in the flue gas stream, it would tend to suppress the formation of D/F. Calcium-based internal scrubber. The conditioning tower used for flue gas temperature control at the discharge of the preheater tower of a preheater or precalciner kiln system initially can be installed as or subsequently retrofitted to become an internal dry scrubber using a slurry of calcium hydroxide as the scrubbing reagent. These systems are effective in the reduction of SO2 emissions and detached plumes (EnviroCare, 2002). Due to inadequate reagent retention time in the conditioning tower, retrofit installations may not be as effective as a properly designed, new installation. The spent reagent that contains oxidized sulfur as sulfite or sulfate salts conveniently becomes a raw material constituent and there is no waste to dispose. In any scrubbing system using abrasive slurry, control of the slurry flow and mechanical maintenance of the system can be problematic, but the relatively high scrubbing efficiency and the lack of waste residue are decided benefits for this system. To the degree that this technology also absorbs the AG precursors to D/F formation, HCl and Cl2, that are present in the flue gas stream, it would tend to suppress the formation of D/F. Pyroprocessing system design. Unique kiln systems of atypical design can take advantage of the inherent properties of the cement manufacturing process to achieve environmental goals under site-specific circumstances. These systems often must use additional energy or suffer a lower production rate than traditional designs but the improved environmental performance and the avoidance of problems associated with pollution abatement equipment occasionally make such designs acceptable to an owner. At one plant there is a unique combination of a low-NOX calciner, a single-stage preheater, and a dryer crusher that exceeded all environmental and production expectations including very low emissions of SO2. In this case, fuel consumption with the attendant NOX and CO2 emissions were higher than would have been experienced with a traditional precalciner kiln system (Vu, 2001). Tailpipe wet scrubber. Based on publicly available permits, tailpipe wet scrubbers using limestone as the scrubbing reagent have been installed on four cement kilns in the recent past. There are no published data detailing the experience to date with these scrubbers. However, the spent reagent (calcium sulfite) must be disposed of or oxidized to calcium sulfate for use in the finish mill of the cement plant as a set regulator in the cementitious product. There may be a wastewater stream that requires treatment before discharge. It is expected that the wet scrubber

23

would remove NH3 and HCl, if any, from the exhaust gas. Carryover of residual sulfuric acid mist and of the scrubbing limestone as PM may present environmental compliance problems.

Potential control technologies.

Mixing air fan. Despite the motion of the rotary kiln and the high velocity of the gas inside the kiln, the gas flow in the calcining zone of the kiln is stratified, i.e., experiences laminar flow. If the high-temperature gas in the calcining zone contains sufficient excess oxygen and is thoroughly mixed, SO2 would be oxidized to SO3 that could then react with the abundance of calcium and alkali metal oxides suspended in the gas stream. The result would be the lowering of SO2 emissions through the capture of sulfur as a solid sulfate in the clinker or in the CKD that is expelled from the kiln system. High-pressure air in the range of a 2-10% replacement of the secondary combustion air can be injected through the shell of the rotary kiln to provide sufficient oxygen for oxidation of SO2 and the kinetic energy necessary for mixing of the flue gas. This technology was developed initially to allow for more complete combustion of solid fuel introduced near the midpoint of the rotary kiln and later was adapted to reduce the generation of NOX. In a limited number of applications, a mixing air fan attached to a rotary kiln also has shown simultaneous reductions in the emissions of SO2, CO, and THC. Conceptually, this technology could be installed on any of the kiln systems for the primary purpose of SO2 emission reduction. In-line raw mill hydrated lime injection. A potential variant of the use of a conditioning tower as a calcium-based internal scrubber is the injection of the calcium hydroxide slurry into an in-line raw mill. Water frequently is injected into a vertical roller mill to improve operation of the mill. If this water were replaced with calcium hydroxide slurry, the flue gas and an effective scrubbing reagent would be intimately mixed within the mill near the optimum reaction temperature to enhance the inherent scrubbing efficiency of the in-line raw mill. To the degree that this technology also absorbs the emissions of the AG precursors to D/F formation, HCl and Cl2, that are present in the flue gas stream, it would tend to suppress the formation of D/F. Fabric filter absorption. Older literature suggests that SO2 is removed from cement kiln flue gas in a fabric filter PMCD. This removal seldom has been observed in practice because the bulk of the material on the filter, i.e., calcium carbonate, is not reactive with SO2 at the temperature and humidity conditions in the fabric filter. If calcium oxide is present on the filter medium, e.g., in an alkali-bypass PMCD, a small but measurable reduction in SO2 concentration in the flue gas may be observed. If a scrubbing reagent, e.g., hydrated lime, were added to the flue gas stream ahead of the PMCD, some adsorption of SO2 might be observed. If the fabric filter is operated at or below the acid dew point, AGs will be removed from the flue gas. However, this practice is not acceptable because severe corrosion and ultimate destruction of the PMCD is a certain result. Sodium-based internal scrubber. This system would be similar in concept to the calciumbased internal scrubber for preheater and precalciner kilns except that a solution of sodium carbonate/sodium bicarbonate derived from naturally occurring trona or manufactured reagents would be used in lieu of the calcium hydroxide slurry in the conditioning tower. Trona is more expensive than hydrated lime but is a more effective reagent. Handling and spraying a solution

24

is always easier than handling and spraying slurry. Care must be exercised that the introduction of sodium into the process does not render the product unmarketable. CKD from an alkali bypass could be wasted to reduce the sodium content of the clinker. The limited use of a sodium carbonate/sodium bicarbonate solution in the conditioning tower might suffice for control of a detached plume that is observed only when an in-line raw mill is down. To the degree that this technology also absorbs the AG precursors to D/F formation, HCl and Cl2, that are present in the flue gas stream, it would tend to suppress the formation of D/F. Calcium/sodium-based internal scrubber. A possible synergetic combination of technologies would be to inject calcium hydroxide slurry into the in-line raw mill during its operation and a sodium carbonate/bicarbonate solution into the conditioning tower when the raw mill was down for maintenance or raw mix inventory control. Some problems with slurry handling would be eliminated, e.g., wear-sensitive nozzles are not required for calcium hydroxide slurry injection into the in-line raw mill, and the addition of sodium to the process and clinker is minimized. To the degree that this technology also absorbs the AG precursors to D/F formation, HCl and Cl2, that are present in the flue gas stream, it would tend to suppress the formation of D/F. Oxygen enrichment. Oxygen enrichment through the use of liquid oxygen (LOX) has been shown to be an effective mechanism for increasing the production of a cement kiln. Because of the cost of purchased LOX or its onsite production, the technology has never been economically justified. Cement kilns are usually fan limited, i.e., the maximum production rate of the kiln is limited by the amount of flue gas that can be moved by the induced draft fan or fans. The introduction of oxygen without the burden of nitrogen from air allows the induced draft fan to handle the combustion products that result from the combustion of additional fuel that, in turn, allows more production. The presence of adequate oxygen in the kiln system should reduce SO2 emissions by oxidizing sulfur to a solid sulfate that is retained in the clinker or expelled from the kiln system with the CKD. Generation of CO at the combustion site should be minimized and easily controlled. The use of LOX in the burning zone of the rotary kiln will have an initial tendency to increase NOX emissions because of a hotter burning zone and increased oxygen at the combustion site. However, if the clinkering temperature requirement is unchanged, the NOX emissions should return to their previous level in a relatively short time when process equilibrium is restored. Dual-alkali process (soda ash/lime). This is a tailpipe scrubber technology that would use a water solution of sodium sulfite and sodium hydroxide in a spray chamber or packed column at approximately 120oF to absorb SO2 and AGs in the flue gas stream immediately following the main or bypass PMCD. The flue gas from a cement pyroprocessing system often would require cooling before this process could be used. Upon exit from the scrubber, the scrubbing liquid would be treated with calcium oxide, calcium hydroxide, or calcium carbonate to precipitate sulfite/sulfate ions and to regenerate sodium hydroxide. The calcium sludge would be removed from the liquid using a filter press or other filtration system and must be disposed as a waste in an appropriate landfill that may or may not be available on site. Water and make-up reagent, sodium hydroxide or sodium carbonate, would be added to the scrubbing liquid that is recirculated to the scrubbing device.

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Thermal decomposition (roasting). Smelting of pyritic metal ores is accomplished by roasting them at 600800oC (11101470oF) to oxidize sulfide sulfur to SO2. This same phenomenon occurs in the upper stages of a preheater tower to generate SO2 from cement raw materials containing small amounts of reduced sulfur. At considerable economic and energy costs, cement raw materials could be roasted outside the normal pyroprocess to liberate the SO2. The liberated SO2 would have to be captured using one of the tailpipe technologies described in this paper. The independent roasting of the raw materials would have the advantage of reducing the volume of flue gas requiring treatment to remove SO2. If present, hydrocarbons also would be liberated and if combustion conditions were inadequate, CO could be generated. Because of the independent thermal process, emissions of CO2 and NOX would increase beyond those experienced by an integrated cement pyroprocess in which the SO2 was generated. Tailpipe dry scrubber. In this technology, a traditional, stand-alone, tailpipe dry scrubber (also known as a spray dryer absorber) would be installed after the main or alkali-bypass PMCD through which the flue gas is passed. A limestone or calcium hydroxide slurry would be used as the scrubbing reagent. Typically, the temperature of the flue gas at the exit of the fabric filter is too low to accomplish drying of the reagent slurry prior to its collection in a fabric filter. Consequently, the flue gas must be reheated with a clean fuel, e.g., natural gas, to accomplish the necessary drying of the reagent. In addition to the production of increased CO2 emissions from the added fuel, there is likely to be an increase in other pollutants, i.e., NOX and CO, resulting from reheating the gas and a need to dispose of spent reagent removed from the fabric filter. In some applications of a spray dryer absorber, activated carbon has been injected upstream of the absorber to control the emissions of D/F (Richards, 2003). Cement kiln dust tailpipe scrubber. There has been a full-scale pilot plant installation of this technology. Flue gas from a wet process kiln was passed through a slurry of CKD, the SO2 absorbing reagent, in a complicated and prohibitively expensive contact device. Reductions in SO2 emissions on the order of 95% were obtained. Crystalline potassium sulfate, a fertilizer constituent, was to have been extracted (leached) from the CKD slurry in commercial quantities. The leached CKD would have been returned to the kiln in slurry form as a reduced-potassium raw material. Problems associated with the crystallization of potassium sulfate were not solved. The expensive contact device and the crystallization problems contributed to the commercial failure of the process. (Young, 2003) This scrubber also would have removed THC, AG, and NH3 from the exit gas, and the potential for formation of a detached plume would have been reduced. This technology would be best suited for wet process kiln systems.

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Control of Nitrogen Oxides

Table 4. Nitrogen Oxides Control Technologies. Control technologies Potential effects Synergetic Existing control technologies Oxygen control (decrease) Indirect firing Low-NOX burner Mid-kiln firing Process improvements Process control improvements Low-NOX calciner Staged combustion Semi-direct firing Mixing air fan Cement kiln dust insufflation Biosolids injection Potential control technologies Fuel substitution Raw material substitution Selective noncatalytic reduction Modified direct firing LoTOX scrubber Oxygen enrichment Flue gas recirculation Selective catalytic reduction Tri-NOX Multi-Chem wet scrubber Water/steam injection Catalytic filtration (ceramic filter) Non-thermal plasma SO2, THC, D/F SO2, AG SO2, CO CO, SO2 NH3, CO2, detached plume, solid catalyst wastes Water discharges CO, CO2 PM Water discharges, ozone slip Fuel/process specific Material specific NH3, detached plume PM SO2, CO, THC CO, CO2, SO2 CO, NH3, detached plume, metals CO2 CO2 Burner/application specific Application specific Project specific Project specific CO CO SO2, CO, product color and quality PM Counteractive

Existing control technologies.

Oxygen control (decrease). For control of NOX originating at the high temperature combustion site in a rotary kiln, a decrease in oxygen (excess air) in the burning zone tends to 27

minimize the generation of thermal and fuel NOX. Both of these mechanisms of NOX formation are oxygen dependent. The reduction in excess air reduces the strength of the oxidizing conditions in the rotary kiln and usually causes an increase in SO2 generated from the fuel used in the main flame. If there is flame impingement on the material in the kiln, i.e., localized reducing conditions, the decrease in oxygen concentration may further exacerbate SO2 generation. The reduction of oxygen concentration at the primary combustion sites in a precalciner kiln system also will tend to reduce the generation of fuel NOX. The decrease in oxygen concentration at combustion sites may cause or increase the generation of CO. There is a small energy benefit for reducing excess air in the system that will result in a slight decrease in fuel consumption and CO2 emissions. The production of cement clinker under generalized or localized reducing conditions usually has deleterious effects on product color and performance. Indirect firing. There are two basic mill systems for preparing and burning solid fossil fuel in cement kilns. The first of these is called a direct-fired system in which hot air from the clinker cooler is used to dry the coal while it is being ground in the mill and to pneumatically transport the powdered coal to the combustion site for immediate combustion. About 20-25% of the air required for combustion is supplied through the coal mill and burner pipe. This air is called primary air. In the second or indirect-fired system, the powdered coal is separated from the drying and transport air by cyclones and/or fabric filters, and is stored in a bin or silo prior to being metered and pneumatically transported by ambient air to the combustion site. In an indirect-fired system, the primary air can be reduced to about 10-15% of the total combustion air. Since the generation of both thermal and fuel NOX is oxygen dependent, the reduction in available oxygen in the flame envelope in an indirect-fired coal system results in a reduction in NOX generation. Indirect coal firing systems generally result in improved thermal efficiency for the kiln system and a reduction in CO2 emissions. Because the solid fossil fuel is separated from the transport air in PMCDs that exhaust to the atmosphere, there is an increase in PM emissions from an indirect-fired system when compared to a direct-fired system with no vent to the atmosphere. A variant of the indirect-fired system uses oxygen-deficient flue gas to dry and transport the coal to the PMCD that separates the powdered coal from the flue gas. The oxygendeficient flue gas is used to inert the coal mill atmosphere for safer coal grinding and has no effect on NOX generation because it is not used as primary air. Low-NOX burner. Several vendors provide adjustable burners with proprietary designs that are intended to reduce NOX generation through the mixing scheme for fuel and primary air by reducing flame temperature, altering turbulence in the flame, and establishing oxygen-deficient recirculation zones in the flame. While these burners have the capacity to alter the flame velocity and shape for process purposes, they have met with mixed success in the documented control of NOX generation. Most often, these burners are installed with an indirect-fired coal system as part of a retrofit project for a direct-fired system or as part of a new pyroprocessing system. At the conclusion of a successful project, it is impossible to sort out the relative contributions of the low-NOX burner and the indirect-fired coal system to the reduction of NOX generation.

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Mid-kiln firing. Although it could be applied to preheater kiln systems3, mid-kiln firing primarily provides for staged combustion in wet or long-dry kiln systems. Once per revolution of the kiln, a single charge of fuel is introduced into the calcining zone through the kiln shell using a gated feed device. As the carbonaceous fuel charge burns in the low oxygen environment of the calcining zone, free radicals are generated that in turn chemically reduce the NOX that was generated in the burning zone to molecular nitrogen (Eddings, 2003). With midkiln firing, there is a risk of increased CO emissions unless there is sufficient residual oxygen, temperature, and mixing downstream of the secondary combustion point in the flue gas flow path. It was for this reason that the mixing-air fan technology was developed. The fuels most often used for this purpose are worn or rejected whole passenger car tires and small containers of combustible hazardous waste. If cost-effective, any solid fuel could be used for mid-kiln firing. If the solid fuel used at mid-kiln has a lower sulfur concentration than the fuel it replaces, there is the potential for reduced SO2 emissions. The intimate mixing of a sulfur-containing fuel and calcining raw mix at the mid-kiln location also may provide an enhanced opportunity for absorption of SO2. Process improvements. Because of the reduced consumption of fuel per unit of production, almost any improvement in an existing kiln system that improves the thermal efficiency of the process will be accompanied by a reduction in long-term NOX emissions per ton of clinker. To help justify the associated capital expenditures, many process improvement projects also result in increased production that tends to negate decreases in overall NOX emissions. When compared to a steam boiler or power plant, the high variability of NOX emissions from a properly operated cement kiln is well known. Process improvements that serve to make the kiln operation more stable without necessarily increasing production also accomplish NOX reductions over the short term, the long term, and per ton of clinker. Any process improvement project should be evaluated for its effect on the generation and emission of all pollutants. Process control improvements. Process control improvements are characterized by the installation of new or better instrumentation and/or process control systems. In older kiln systems, the improvement might mean replacing an analog process control system with a digital computer. In newer kiln systems with an adequate digital computer, the use of one of the expert or fuzzy logic control systems and the necessary process instrumentation could represent a significant process control improvement. In essence, the expert systems are satellite computers that guide the process computer in controlling the kiln system. They are able to detect subtle changes in the process and to take corrective action more rapidly than the central control room operator. The common purposes of most process control improvements on kiln systems are to improve thermal efficiency and the clinker production rate. However, if a process control improvement project simply results in a more stable pyroprocessing system, lower NOX emissions over the short term, the long term, and per ton of clinker will result. Any process control improvement project should be evaluated for its overall effect on the process and on the generation and emission of all pollutants.
The initial purpose of mid-kiln firing was to burn fuel at the point in the process with the maximum requirement for thermal energy input, i.e., calcination of the calcareous component. In the case of many preheater kiln systems and all precalciner kiln systems, the majority of this energy requirement has been satisfied prior to the rotary kiln in the material flow path. In addition, the temperature of the flue gas inside the rotary kiln at the mid-kiln firing access point for precalciner kiln systems is too hot for the fuel injection apparatus to survive.
3

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Low-NOX calciner. All vendors of cement pyroprocessing systems offer proprietary calciner designs that carefully control the mixing sequence of fuel, air, and raw materials in the calciner vessel. The common feature of all these systems is an oxygen-deficient initial combustion zone in which free radicals are generated that subsequently react with NOX to form molecular nitrogen and other reaction products (Miller and Bowman, 1989). At the operating conditions found in the calciner, CO also is formed. The initial combustion zone is followed in the gas flow path by a secondary combustion zone in which residual CO in the flue gas is oxidized to CO2. These designs have worked quite well in new installations. When applied to calciner replacement or retrofit projects, physical restraints often limit the ability of the vendor to install a fully functional low-NOX calciner. The result may be an unpredictable and disappointing reduction in NOX generation in the calciner. In all these designs, there is the possibility of increased emissions of residual CO if the downstream oxidation is not complete. Staged combustion. The function of staged combustion (sometimes called secondary firing) in preheater or precalciner kiln systems is to develop a reducing zone in the flue gas flow path after the burning zone in which free radicals produced during staged combustion of hydrocarbon fuels react with NOX from the burning zone to form molecular nitrogen and other reaction products. The most prevalent location for staged combustion is in the riser duct between the discharge of the rotary kiln and the calciner vessel. Typically, natural gas is the most convenient fuel but pulverized (powdered) coal, used oil, and waste-derived fuels also are used for this purpose. Worn or rejected whole passenger car tires also are inserted into the feed end of the rotary kiln to accomplish NOX reduction through staged combustion. In preheater kiln systems, there is a high probability of increased CO emissions unless there is a source of air (oxygen) to oxidize residual CO downstream of the staged combustion site in the flue gas flow path. In precalciner kiln systems, the residual CO from staged combustion has an opportunity to be burned in the calciner vessel so the probability of increased CO emissions resulting from staged combustion is reduced but not necessarily eliminated. Semi-direct firing. In one way or another, semi-direct firing systems mechanically separate the powdered coal in the coal mill exhaust from the coal drying and transport air to provide for better combustion control through independent metering of the coal being fed to the kiln and to sometimes reduce the quantity of primary air used in the main burner pipe. In the basic semidirect firing system, the entire coal mill exhaust air stream is used as primary air. To reduce the primary air volume, only a portion of the dedusted air discharged from the separation device, e.g., a cyclone, may be used as primary air in the main burner with the balance of the air being directed to the kiln hood to function somewhat as secondary air and to provide for consumption of the residual coal in the air stream (Hansen, 2003). In some situations, the dedusted coal mill exhaust air stream in excess of primary air requirements may be recirculated to the coal mill system. Semi-direct firing systems for solid fossil fuels have the benefit of potentially reducing NOX generation through a reduction in primary air for the main kiln burner while avoiding the source of PM emissions from the coal mill PMCD found in an indirect-fired system. When compared to a direct-fired system, the reductions in NOX generation attributed to a semi-direct system can be as great as those that would be experienced with an indirect-fired system (Hansen 2003).

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Mixing air fan. If the flame at the discharge end of a rotary kiln could be operated with reduced oxygen at the combustion site, the generation rate of thermal and fuel NOX would be less than if a large excess of oxygen were present. In addition, free radicals would be formed in the flame that could react with NOX to form molecular nitrogen in the appropriate temperature window located downstream of the burning zone in the flue gas flow path. Excess CO in the flue gas that also is generated by the main flame requires oxidization prior to discharge to the atmosphere. High-pressure air, in the range of a 2-10% replacement of the primary combustion air, can be injected through the shell of the rotary kiln and into the calcining zone to provide sufficient oxygen to convert the excess CO to CO2, and to better mix the gas within the rotary kiln. This technology was developed initially to allow for more complete combustion of solid fuel introduced through the mid-kiln firing technology and was later adapted for the reduction of NOX generation in a rotary kiln. In a limited number of applications of a mixing air fan to a rotary kiln, simultaneous reductions in the emissions of SO2, CO, and THC have been demonstrated. Conceptually, this technology could be installed on any of the kiln systems for the primary purpose of NOX emission reduction and would not interfere with other pollution control technologies. Cement kiln dust insufflation. As a means of recycling usable CKD to the pyroprocess, CKD sometimes is injected or insufflated into the burning zone in or near the main flame. The presence of these cold solids within or in close proximity to the flame has the effect of cooling the flame and/or the burning zone thereby reducing the formation of thermal NOX. The insufflation process is somewhat counterintuitive because a basic requirement of a cement kiln is a very hot flame to heat the clinkering raw materials to about 1480oC (2700oF) in as short a time as possible. Because there is an increased requirement for thermal energy in the burning zone when insufflation is employed, it is not an attractive technology for recirculation of CKD except in wet kiln systems where other options are not available, practical, or productive. There are more efficient ways to recycle CKD in dry kiln systems. Because of the increased requirement for thermal energy, CO2 emissions would increase. Because of the disruption of the flame, CO generation also may increase and the generation of free radicals could possibly result in additional NOX reduction. The injection of a high-sulfur material, i.e., CKD, in the vicinity of the flame may increase SO2 generation and emission if localized reducing conditions are present. As a variant to CKD insufflation, essentially the same effects have been observed when raw material mix has been insufflated on an experimental basis. The insufflation of raw material mix on a commercial scale probably would not be acceptable as a NOX control technology because of the thermal inefficiency associated with the practice. Biosolids injection. The injection of biosolids from municipal wastewater facilities into the proper temperature window in the preheater tower serving a preheater or precalciner kiln system is a variant of the selective noncatalytic reduction (SNCR) system that is discussed in a later section. The biosolids provide a source of NH3 and some fuel value for the process. The NH3 reacts with NOX that has been formed in the kiln or calciner to form water and elemental nitrogen. If the NH3 is not consumed fully by available NOX, excess NH3, i.e., an ammonia slip, will be emitted from the stack to increase the potential for a detached plume. Ammonia also is a precursor pollutant to the formation of regional haze. Unlike most other control existing technologies for cement kilns, biosolids injection uses a potential gaseous pollutant of concern in

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an effort to control the emissions of another pollutant. Because of the water that accompanies the biosolids, there is an increase in primary fuel requirements per ton of clinker that counteractively tends to increase the potential for NOX generation. If the kiln system is fan limited, the additional water vapor reduces the maximum production rate of the kiln. Because the biosolids are burned in a low-oxygen environment, there may be an increase in the emissions of CO. If there are metals present in the biosolids, the potential exists for the more volatile species to be emitted from the kiln system.

Potential control technologies.

Fuel substitution. In wet, long dry, and preheater kiln systems without NOX control technologies, the top-down order of fuels for NOX generation is natural gas, oil, and coal. Thermal NOX dominates the process of NOX generation in the rotary kiln. Natural gas has a higher potential flame temperature than oil or coal. In the calciner vessel of a precalciner kiln system, the top-down order of fuels for NOX generation is reversed. Although thermal NOX generation continues to dominate in the burning zone of the rotary kiln in the precalciner kiln system, only about 40% of the thermal energy for the process is required at that location. In the calciner, where the balance of the thermal energy input is accomplished through relatively low temperature combustion, fuel NOX dominates NOX generation. A NOX reduction strategy could be developed using an available and cost-effective fuel or a combination of fuels with the lowest potential for NOX generation. Because about a third of the cost of cement manufacture is energy related, the selection of fuel is always cost-sensitive. As noted previously, a change in fuel could have an effect on the generation or emission of other pollutants. For example, a change to coal from natural gas in a wet kiln system has the potential to increase the emissions of SO2. Raw material substitution. It has been shown in the laboratory that nitrogenous compounds present in some cement raw materials have the potential to generate feed NOX upon heating at temperatures of 300800oC (5701470oF) (Gartner, 1983). Slow heating in this temperature range, such as would be found in a wet or long-dry kiln, appears to maximize the potential formation of feed NOX. The rapid heating found in a preheater tower appears to result in a much lower potential for NOX generation. It is very difficult to identify this phenomenon in the field because of the other sources of NOX generation in a cement pyroprocess (Penta, 1999). The chemistry of the raw material mix can be altered chemically to produce a softer burning mix, i.e., a mix in which the desired clinker minerals are formed at a lower temperature, by selectively replacing one of the siliceous, argillaceous, or ferriferous raw materials. Although the nominal value for clinkering temperature is 1480oC (2700oF), the actual temperature can range from about 1400oC (2550oF) to about 1550oC (2820oF) depending on the chemistry of the raw material mix and other factors. A softer burning raw material mix results in a lower flame temperature requirement and a relatively cooler burning zone that will result in the generation of less thermal NOX. The proof of the efficacy of raw material substitution for NOX control only can be shown in site-specific trials over several months. A change in raw materials can always result in unintended changes in pollutant emissions, e.g., the new raw material might contain sulfide sulfur that would cause an increase in emissions of SO2. Changes in raw materials through selective purchasing, selective quarrying or judicious blending should not preclude the application of other technologies.

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Because cement plants are normally located at or near their sources of raw materials, there are often critical economic limitations to the practicability of substituting raw materials to produce a softer burning raw mix or to reduce the nitrogen content of the raw materials. Selective noncatalytic reduction. In the temperature window of 870-1090oC (1600 to 1995oF), NH3 reacts with NOX to form water and molecular nitrogen. Above this temperature range, the NH3 is oxidized to NOX. Below this temperature range, the reaction is too slow and unreacted NH3 may be emitted from the pyroprocess. As the CO concentration at the reaction site increases, the optimum temperature for the reaction decreases. (Brouwer, Heap, Pershing and Smith, 1996; Eddings, 2003). This temperature window generally is available in the flue gas stream at a location in the lower stages of the preheater tower in a preheater or precalciner kiln system. In a wet or long-dry kiln system, the temperature window is located well inside the rotary kiln and physically cannot be accessed readily. The NH3 could be delivered to the preheater tower through the use of anhydrous NH3, or an aqueous solution of NH3 (ammonium hydroxide) or urea. Anhydrous NH3 is reported to be more effective as a reagent but safety considerations suggest that the solutions of NH3 or urea are more acceptable reagents. A concern about application of SNCR technology is the breakthrough of unreacted NH3 as an ammonia slip and the increased potential for the formation of a detached plume and a contribution to regional haze. Ammonia slip is certain to result from the superstoichiometric addition of NH3 while attempting to achieve the maximum reduction of NOX emissions. Unlike most other control technologies for cement kilns, SNCR uses a gaseous pollutant of concern in an effort to control the emissions of another pollutant. Depending on the physical arrangement and dimensions of the calciner and the adjoining preheater stage, the installation of SNCR on an existing precalciner kiln system may be problematic. Because of the requirement for oxygen as a constituent in the SNCR reaction, there is concern that SNCR and staged combustion in a lowNOX calciner are incompatible technologies, i.e., there may be an oxygen deficiency at the location in the process of the appropriate temperature window. SNCR has been used successfully on cement kiln systems in Europe but only recently has been applied as a full-time control technology in the United States on a precalciner kiln system (Williams, 2003). Modified direct firing. In a procedure similar to semi-direct firing, solid fossil fuel is mechanically separated from the coal mill exhaust air stream with a high-efficiency separator and briefly stored prior to being metered to the kiln. The dedusted coal mill exhaust air from the high-efficiency separator is used as primary air. Unlike other systems, however, the coal mill system fan is of variable speed so that the volume of primary air can be maintained at a constant ratio to the coal feed rate. A firing system of this type would be particularly beneficial for use on a kiln system wherein variable quantities of waste-derived fuel are burned and the coal firing system is required to provide the balance of the required thermal energy. Because of the decoupling of the powdered coal and the coal mill system air stream, the system provides for a potentially reduced percentage of primary air and a resulting reduction in the rate of NOX generation in the main flame. The modified direct-fired system provides the combustion control benefits of an indirect-fired system without the PMCD exhaust associated with an indirect-fired system (Hansen, 2003). LoTOx scrubber. The LoTOx scrubber is a proprietary low-temperature tailpipe device that uses water as the scrubbing reagent. In a series of discrete steps, the flue gas would be

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quenched (if necessary) to lower the temperature to below 120oC (250oF), treated with ozone to rapidly oxidize NO and NO2 to nitrogen pentoxide (N2O5), and scrubbed with water to convert the N2O5 to nitric acid. Unreacted NO2 would form nitrous acid in the water scrubber. It is claimed that ozone reacts preferentially with NOX and that there would be no competition with residual CO and SO2 in the flue gas for the available ozone. Because the ozone would be produced on demand in response to the NOX concentration in the scrubber feed stream, there should be little unreacted ozone in the scrubber discharge gas but ozone slip is a possibility. If SO2 and SO3 are present in the flue gas, there should be measurable removal of these pollutants from the flue gas by the water scrubber. The effluent from the scrubber would have to be treated with a caustic to raise the pH before discharge. Removal of nitrous and nitrate salts also might be required. Alternatively, the scrubber could use a caustic solution to simultaneously accomplish scrubbing and neutralization. Oxygen enrichment. Through the use of oxygen enrichment, an increase in the concentration of oxygen at the primary combustion site in a rotary kiln would tend to increase the generation of NOX on a short-term basis. Because of the corresponding reduction in the amount of relatively cool secondary air from the clinker cooler, the temperature in the burning zone would tend to increase that would result in an increase in NOX generation. However, if the required clinkering temperature does not change and the process returns to equilibrium, there is no apparent reason for the NOX emissions to change. Therefore, the use of oxygen enrichment to reduce NOX emissions would appear to be counter-indicated. The use of LOX as a complement to other NOX reduction technologies, e.g., staged combustion, might have a beneficial outcome. In a pilot scale application, the amount of LOX added to the kiln was adjusted to provide a maximum of only 22% oxygen by volume in the combustion air to stabilize kiln operation with no anticipated increase in clinker production. Any time that kiln operation is stabilized, total NOX emissions tend to decrease over the long term and per ton of clinker. At moderate oxygen enrichment rates, e.g., 28% oxygen by volume in the combustion air, the previous amount of relatively cool secondary combustion air from the clinker cooler is reduced; therefore, the burning zone temperature is increased for the same amount of fuel and the potential for immediate thermal NOX generation increases. Unless carefully controlled, the addition of LOX also can serve to increase long-term thermal and fuel NOX generation simply because of increased oxygen at the combustion site. High rates of oxygen enrichment, e.g., 35% oxygen by volume in the combustion air, have resulted in the rapid elimination of clinker coating and the deterioration of the burning zone refractory (Willis, 2002). Flue gas recirculation. Flue gas recirculation would involve the use of post-combustion flue gas extracted from an appropriate location in the pyroprocess in lieu of primary air in the burner of the rotary kiln. The intent would be to initially burn fuel in oxygen-deficient conditions to lower the thermal and fuel NOX formation rates. An increased flow of secondary air from the clinker cooler would be required to supply sufficient oxygen to completely burn the fuel. The increase in secondary air would tend to cool the burning zone and to further contribute to thermal NOX reduction. The recirculated flue gas passing through the main burner would replace an equal volume of oxygen-laden primary air; therefore, in a fan-limited kiln system, the total amount of fuel that can be burned and the resulting clinker production rate would be reduced. A reduction in the clinker production rate is seldom an acceptable outcome of any process change. Because the flame in the kiln would become long and lazy, the temperature profile in the kiln

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would change and could result in a crystal structure in the clinker that is detrimental to product quality. To lower the potential for fire and explosion, flue gas is sometimes used in an indirectfired coal mill system to inert the mill and the PMCD; however, flue gas is seldom, if ever, used in lieu of primary air in a direct-fired coal mill system. Flue gas recirculation would have the potential to increase the generation of CO and SO2 because of the oxygen deficiency at the primary combustion site. There is no advantage to using flue gas recirculation in a calciner because combustion in this vessel already is accomplished at relatively low temperature with a minimum quantity of available oxygen. Selective catalytic reduction. Selective catalytic reduction (SCR) has not been applied to cement kiln systems in the United States. However, in some industrial applications, SCR is an established NOX reduction technology that uses the well-known reaction between NH3 and NOX. A catalyst is used to accomplish the reaction in a lower temperature window, 300-450oC (570 840oF), than is required in the SNCR technology. To prevent blinding and fouling of the catalyst, the reaction must be conducted in a flue gas stream that is essentially free of PM and certain metals. Therefore, SCR would be a post-PMCD technology if applied to a cement kiln. The flue gas would require reheating because the temperature of the flue gas stream from a PMCD serving a cement kiln system is usually less than 204oC (400oF) because of D/F control requirements. An attendant increase in the emissions of CO2 and other combustion products will occur as a result of the reheating. Fouling of the catalyst may occur from SO2 in the flue gas; therefore, a clean fuel, e.g., natural gas, would be appropriate for the flue gas reheating. In addition, normal concentrations of SO2 in the flue gas from a cement kiln system could deleteriously affect the catalyst. Consequently, an SO2 reduction technology might have to be applied to the process or to the flue gas in advance of the SCR application. In SCR, there is the possibility of ammonia slip that contributes to the formation of a detached plume and to regional haze. Ammonia slip is certain to result from the superstoichiometric addition of NH3 while attempting to achieve the maximum reduction of NOX emissions. Unlike most other control technologies for cement kilns, SCR uses a gaseous pollutant of concern, NH3, in an effort to control the emissions of another air pollutant. At some site-specific elapsed time, the catalyst will require replacement and will result in a new solid waste stream from a cement plant using this technology. Tri-NOX Multi-Chem scrubber. Sodium hydroxide, sodium monosulfide, sulfuric acid, and sodium chlorite are used as the scrubbing reagents in the Tri-NOX Multi-Chem scrubber, a proprietary low-temperature tailpipe system. In a series of scrubbing towers, the flue gas is quenched to lower the wet bulb temperature, NO is oxidized to NO2, and the NO2 is subsequently reduced to molecular nitrogen and water. The system cannot be blinded, there is no catalyst to foul, and reheating of the flue gas is not required. However, there is a wastewater stream of elevated pH and high salt loading that must be treated prior to discharge. Although the system has the potential to meet any stack conditions, perhaps it is best suited to relatively small installations with a low flue gas flow rate and high NOX concentrations. The Tri-NOX MultiChem system also could be expected to concurrently reduce emissions of SO2 and AGs. Water/steam injection. The injection (insufflation) of water or steam into the main flame of a rotary kiln can act as a heat sink to reduce the flame temperature and the resulting generation of thermal NOX. Because of its latent heat of vaporization, water would be more effective than

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steam. However, for a process that requires a high flame temperature to accomplish clinker formation, a significant reduction in flame temperature without compensating benefits is counterintuitive and an obvious waste of energy. However, one white (colored) cement plant located in an area of sensitivity for NOX emissions attributes a fortuitous reduction in NOX generation to the spraying of water on the clinker at the discharge of the rotary kiln to maintain the color of the clinker. No doubt, the resulting steam suppresses the flame temperature but at a significant energy penalty that results in higher emissions of CO2 (Johnson, 2003). Because of product color and quality concerns, and the increased consumption of thermal energy, it is highly unlikely that the water spray system would be acceptable in a gray cement kiln. If the flame temperature is sufficiently quenched, the generation of CO can increase and/or the clinkering process will cease. Catalytic filtration (ceramic filter). This technology is a variation of the SCR process and requires the incorporation of a catalyst within or upon a PM filter medium at a process location requiring the separation of PM from the flue gas stream, i.e., at a tailpipe location. Because of the relatively high temperature required for NOX reduction using NH3 as a reagent in the SCR process [300-450oC (572842oF)], currently available filter fabrics would be destroyed. A ceramic filter medium would be necessary to accomplish simultaneous high-temperature filtration and NOX reduction. At the pilot plant level, ceramic filters (without catalysts) have been designed for gas streams at a temperature of 600oC (1110oF). The ceramic filter media can replace the bags in a pulse-jet fabric filter and use the pulse-jet cleaning methodology. Because of the high solids loading in untreated flue gas from a cement pyroprocessing system, the catalyst on both filtration media would be subject to blinding. To reduce the PM loading on the catalytic filter, a mechanical PM separator, e.g., a cyclone, could be installed ahead of the catalytic filter. The catalyst also would be subject to fouling from several constituents in the flue gas. The development of a catalyst that operates at a lower temperature and/or a reagent other than NH3 would make this technology more applicable to cement kilns. Non-thermal plasma. Plasma is the fourth state of matter, i.e., excited atoms and ions in the form of ionized gas. Commonly, the plasma state is reached by thermal means but non-thermal means, e.g., microwaves, electron beams and electrical discharges, can be used for such practical purposes as ozone generation and the decomposition of gaseous pollutants. Substantial research has gone into the application of non-thermal plasma to the reduction of soot and NOX emissions from diesel engine exhausts. The future application of non-thermal plasma to the removal of NOX from the flue gas of a cement kiln would likely take a similar approach. The flue gas would pass through a non-thermal plasma generator where the NOX would be converted to inert species, e.g., molecular oxygen and nitrogen, or to a treatable specie, e.g., nitrogen dioxide, that could be efficiently reacted with a suitable reagent. Non-thermal plasma is a tailpipe technology that might not compete with other tailpipe technologies and would be compatible with NOX source reduction technologies. Non-thermal plasma has the potential to minimize or reduce other pollutants from cement pyroprocessing systems, e.g., VOC, D/F and SO2.

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Control of Organics
Table 5. Organic Control Technologies. Control technologies Potential effects Synergetic Existing control technologies Inherent process characteristics (time, temperature, and turbulence) Excess air (increase) Raw material substitution Pyroprocessing system design Mixing air fan Regenerative thermal oxidizer CO, NOX, SO2 CO, D/F detached plume Potential control technologies Thermal desorption (roasting) Thermal oxidation Recuperative thermal oxidation Wet electrostatic precipitator Ultraviolet light Catalytic oxidization Oxygen enrichment Granular activated carbon adsorption Powdered activated carbon adsorption CO, D/F CO, D/F SO2, NOX, PM, AG, NH3, D/F, detached plume D/F CO CO, SO2 NOX, SO2, D/F, metals NOX, SO2, D/F, metals SO2, CO, NOX CO2, NOX CO2, NOX Waste disposal, water treatment CO CO2, NOX NOX Waste disposal, high reagent consumption D/F, Waste disposal, high reagent consumption NOX, CO2, SO3, AG, waste disposal CO CO, SO2 Material specific Process specific NOX, CO2 Counteractive

Existing control technologies.

Inherent process characteristics (time, temperature and turbulence). Any cement pyroprocessing system possesses the three Ts of combustion, i.e., adequate time at high temperature with sufficient mixing (turbulence) to fully burn the organic compounds comprising all commonly used fossil fuels and most alternative fuels, e.g., waste-derived fuel. In unusual circumstances, the systems may be altered to more fully utilize the inherent characteristics of the pyroprocess. An example would be the application of a mixing air fan to increase postcombustion turbulence in a rotary kiln to fully oxidize organic PICs. Excess air (increase). To provide for maximum thermal efficiency, the oxygen concentration in the flue gas at the feed end of a rotary kiln and/or the exit of the preheater tower normally are held as close as possible to 1%. Because of system-specific conditions, this oxygen concentration may be insufficient to allow for complete combustion, and organic PICs could be

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generated at the combustion site. A slight increase in the amount of air passing through the kiln system is often adequate to reduce the excess emissions of organic compounds. An increase in oxygen at the combustion site tends to increase thermal and/or fuel NOX. Additional fuel is required to heat the excess air to combustion temperatures and results in a slight increase in CO2 emissions. The excess air would tend to reduce emissions of SO2 and CO. Raw material substitution. If the cement raw materials contain organic constituents that are volatilized in the pyroprocess prior to reaching combustion temperatures and are emitted as organic pollutants, an effective control strategy is to replace the raw material causing the problem through selective purchasing, selective quarrying or judicious blending. At many cement plants, this technology is not possible due to the unavailability of cost-effective, substitute raw materials. Any change in raw materials for the purpose of pollution control should be evaluated for its effect on the process and other pollutants. Pyroprocessing system design. Unique kiln systems of atypical design can take further advantage of the inherent properties of the cement manufacturing process to achieve environmental goals under site-specific circumstances. The systems often require compromises in production rate, energy consumption, and environmental performance. An example of a successful design is the use of a calciner with a single-stage preheater to immediately subject the raw materials to process conditions sufficient to burn the organic material prior to its vaporization or pyrolysis. In this case, fuel consumption and CO2 emissions would be higher and the production rate would be lower than would be experienced with a traditional precalciner kiln system. Depending on raw materials and process conditions, emissions of NOX and SO2 may well increase because of this process design. Other nontraditional designs will present their own sets of emission characteristics and process compromises. Mixing air fan. This technology initially was developed to allow for more complete combustion of solid fuel introduced near the midpoint of the rotary kiln. Organic PICs generated by the main flame or by mid-kiln firing of solid fuel require destruction prior to discharge of the flue gas to the atmosphere. High-pressure air in the range of a 2-10% replacement of the primary combustion air can be injected through the shell of the rotary kiln into the calcining zone to provide sufficient oxygen to burn the organic compounds and to better mix the flue gas within the rotary kiln. In a limited number of applications of a mixing air fan to a rotary kiln, simultaneous reductions in the emissions of SO2, CO, and NOX have been demonstrated. Conceptually, this technology could be installed on any of the kiln systems and would not interfere with other pollution control technologies. Regenerative thermal oxidizer. The most thermally efficient of the tailpipe thermal oxidizers is a regenerative thermal oxidizer (RTO). As applied to a cement kiln, a RTO consists of several modules, each of which treat an aliquot of the post-PMCD flue gas by reheating it to about 870oC (1600oF) with an open flame and sufficient oxygen to oxidize CO, hydrocarbons and/or odor causing constituents. To minimize collateral pollution, a clean fuel such as natural gas has been the choice for use in an RTO. The heat from the treated flue gas is captured in one of two porous heat sinks in each module. The untreated flue gas is passed through a hot heat sink to recover heat prior to the application of thermal oxidization. Upon dissipation of the heat

38

in the initial module, a system of valves quickly reverses the roles of the heat sinks. The process repeats itself through alternative heating and cooling of the heat sinks. The application of an RTO to a cement kiln system appears to require the consideration of additional pollution abatement technologies. The operating temperature of an RTO strongly encourages the conversion of SO2 in the flue gas to SO3. So that SO3 generation is minimized, a common approach is to apply a wet limestone scrubber ahead of the RTO to remove as much SO2 as possible from the flue gas. The wet scrubber also could be expected to remove NH3, a component of many detached plumes, from the flue gas. The spent reagent from the wet scrubber must be disposed of or fully oxidized to calcium sulfate for use in the finish mill of the cement plant. The use of a wet scrubber requires even more energy to reheat the flue gas and introduces sufficient humidity to the RTO to require materials of construction that resist aggressive corrosion at temperatures below the acid dew point. If necessary, a wet ESP can be applied to the flue gas following the RTO to further reduce SO3 emissions. An alternative approach would be to use one or more of the pre-PMCD SO2 reduction technologies suitable for cement kiln systems to eliminate the need for the wet scrubber. At the operating temperatures of an RTO, D/Fs in the flue gas would be subject to destruction. In conjunction with an RTO, the use of high-intensity light near the ultraviolet wavelengths has the potential to increase the destruction efficiency of THCs in the flue gas (Richards, 2003). The combustion of additional fuel in the RTO will result in additional emissions of CO2 and NOX.

Potential control technologies.

Thermal desorption (roasting). Cement raw materials could be heated in an independent device to volatilize organic compounds prior to introduction of the raw materials into a cement kiln system. To avoid the application of organic and CO emission control technologies, the desorption device would have to operate with adequate combustion conditions including high temperature and excess oxygen. If sulfide sulfur were present in the raw materials, it probably would be roasted to SO2. Because of the independent thermal process in the roaster, emissions of CO2 and NOX would increase beyond those experienced by an integrated pyroprocess in which the hydrocarbons were volatilized. Thermal oxidation. Thermal oxidation would involve the reheating of the flue gas to temperatures of 760870oC (14001600oF) in the presence of sufficient oxygen to achieve complete destruction of any organic compounds present in the flue gas. Because of its inherent inefficiency, thermal oxidization is seldom applied as a tailpipe technology on large-scale processes, e.g., cement kiln systems. To derive benefit from the additional heat input required by thermal oxidization, an application of thermal oxidization in the gas flow path prior to the raw mill in an in-line kiln/raw mill system is conceptually possible. To minimize collateral pollution, a clean fuel, e.g., natural gas, would be the likely choice for use in the thermal oxidization. At the operating temperature of a thermal oxidizer, any D/Fs in the flue gas stream would be subject to destruction. In conjunction with thermal oxidation, the use of high-intensity light near the ultraviolet wavelengths has the potential to increase the destruction efficiency of THCs in the flue gas. Because of the additional consumption of fuel, increases in the emissions of CO2 and NOX would be unavoidable when compared to the pyroprocess without application of thermal oxidization.

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Recuperative thermal oxidation. In the application of recuperative thermal oxidization, the thermal efficiency of thermal oxidization is improved through the use of a countercurrent gas-togas heat exchanger in which heat from the treated flue gas is transferred or recirculated to the untreated flue gas. Recuperative thermal oxidization has the additional potential to reduce CO concentrations in the flue gas and would result in additional emissions of NOX and CO2 because of the additional fuel combustion that is required to raise the flue gas to an effective temperature. Recuperative thermal oxidization is less thermally efficient than an RTO but operates at a temperature sufficient to cause the destruction of D/F. In conjunction with recuperative thermal oxidation, the use of high-intensity light near the ultraviolet wavelengths has the potential to increase the destruction efficiency of THCs in the flue gas. Wet electrostatic precipitator. Several vendors supply proprietary wet ESPs. These devices are similar in operating principle to a dry ESP except that they operate at a temperature well below the boiling point of water, and water is used to flush the pollutants from the collecting plates. Wet ESPs frequently are used to collect acid gases and mists from a variety of sources. Vendors of wet ESPs claim that they are effective in the collection of condensed organic material, submicron PM, volatile metals, NH3, and D/F. In some applications, reductions in the emission of SO2 and NOX also are claimed. If applied to a cement kiln system, there must not be any cement minerals in the flue gas. Otherwise, there will be a buildup of hydrated cement in the wet ESP that will cause the ESP to fail and require manual cleaning. A process location following a wet kiln, a long-dry kiln, or an alkali bypass would not be feasible because cement minerals will be present in the PM. A wet ESP might function following a preheater or an inline raw mill. Ultraviolet light. Ultraviolet light has the ability to initiate free-radical chain reactions in flue gas streams containing NOX, CO and water vapor that alter/destroy the chemical bonds of the organic compounds participating in the reactions. Through the use of intense ultraviolet light in an appropriate low-temperature location following a PMCD, it is conceivable that flue gas from a cement kiln system could be treated to convert some undesirable organic compounds, e.g., formaldehyde, to CO2, water and innocuous organic compounds. Because they are organic compounds, the concentration of D/Fs in cement kiln flue gas also might be reduced upon exposure of the gas stream to ultraviolet light. Because CO is a necessary reagent for the freeradical reactions to occur, excess CO may be emitted with the flue gas. Catalytic oxidation. Various catalysts could be used to enhance thermal oxidation or recuperative thermal oxidization by allowing the destruction of non-halogenated organic compounds at a lower temperature, e.g., 310-370oC (590-700oF). Typically, these catalysts would be contained on a substrate in the form of a grid in the flue gas stream. This technology currently is applied on a much smaller scale than would be required for a cement kiln system. A RTO also could be augmented with catalysts to form a regenerative catalytic oxidizer. The typical problems involving the blinding and fouling of catalysts by PM, SO2, and chlorine would be experienced in the application of this technology. Because of the additional consumption of fuel, increases in the emissions of CO2 and NOX are unavoidable when compared to a pyroprocess without application of catalytic oxidation. It is likely that CO in the flue gas also would be oxidized to CO2 through the use of this technology.

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Oxygen enrichment. This technology could reduce generation of organic PICs by improving combustion efficiency in the rotary kiln or calciner but would probably be ineffective in the reduction of THC emissions that result from evaporation of organic compounds from raw materials. The use of LOX in the high-temperature burning zone tends to increase the generation of thermal and fuel NOX and to decrease the generation of CO and SO2. The use of LOX in the calciner would tend to increase the generation of fuel NOX and to reduce the generation of CO. Granular activated carbon adsorption. Granular activated carbon (GAC) is made from many carbon-containing materials. For large-scale applications in the United States, e.g., cement kilns, the raw materials of choice would be wood, bituminous coal, or lignite. After carbonization, GAC is processed to increase the internal surface contact area through the creation of pores and channels in each granule. GAC would be contained in thick beds inside vessels through which flue gas would be passed. The nonselective absorption on and within GAC of the organic compounds, SO2, NOX, D/F, and metals that are contained in cement kiln flue gas could result in rapid depletion of the adsorbent and breakthrough of the organic pollutants. Depending on economic factors and the adsorbed constituents, GAC can be regenerated on site or sent to a specialized offsite location for regeneration. In some cases, the spent GAC could be classified as a hazardous waste because of adsorbed constituents of concern. The collected constituents that are removed from spent GAC must be collected, destroyed, recycled, or disposed. Depending on the adsorbed constituents, spent GAC could be burned as supplemental fuel in a cement kiln. The generation of CO2 or other pollutants of concern during the manufacture of GAC should be taken into account when considering the use of GAC. Powdered activated carbon adsorption. Essentially the same processes produce powdered activated carbon (PAC) and GAC except that with PAC the adsorbent is in the form of a very fine powder with high surface area. Rather than being placed in adsorbing beds, PAC would be injected into and intimately mixed with the flue gas. PAC would adsorb the same constituents as GAC but might not be fully saturated in the available contact time, i.e., poor sorbent utilization. If PAC were injected ahead of the main or bypass PMCD, then the used PAC would become part of the raw material stream, or of the disposed or recirculated CKD. If PAC were in the raw material or recirculated CKD, organic compounds and other volatile constituents, including metals, adsorbed by the PAC would contribute to the building of a circulating load within the pyroprocess. At some point in time, the circulating load would reach equilibrium and emissions of the pollutants of concern would resume at the rate of generation or introduction into the process. The inclusion of used PAC in the CKD would avoid the problem of volatile pollutant recirculation, but the disposal or beneficial use of the CKD could be compromised because of the PAC itself and/or the adsorbed pollutants in the PAC. If PAC were injected into the flue gas after the main PMCD, the used PAC would be collected in a tailpipe PMCD and disposed. It is possible that the used PAC would be classified as a hazardous waste because of adsorbed constituents of concern. Depending on the adsorbed constituents, the used PAC could be burned as supplemental fuel in the cement kiln. If the used PAC is free of PM from the cement pyroprocess, potentially it could be regenerated and reused. In some applications, it has been observed that the use of PAC contributes to the formation of D/F (Richards, 2003). The generation of CO2 or other pollutants of concern during manufacture of PAC should be taken into account when considering the use of PAC.

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Control of Carbon Monoxide

Table 6. Carbon Monoxide Control Technologies. Control technologies Potential Effects Synergetic Existing control technologies Good combustion practice Excess air (increase) Raw material substitution Pyroprocessing system design Mixing air fan Regenerative thermal oxidizer NOX, CO2, SO2, THC THC, SO2 Material specific Process specific NOX, SO2, THC THC, D/F detached plume Potential control technologies Thermal oxidation Recuperative thermal oxidation Catalytic oxidation Oxygen enrichment THC, D/F THC, D/F THC THC, SO2 NOX, CO2 NOX, CO2 NOX, CO2 NOX NOX, CO2, SO3, AG, waste disposal NOX, CO2 Counteractive

Existing control technologies.

Good combustion practice. The most prevalent technology used for control of CO generation in cement kiln systems is good combustion practice. At each combustion site, adequate time, temperature, and turbulence are provided to make certain that the carbon component of the fuel is fully oxidized to CO2. Good combustion practice contributes to maximum thermal efficiency, reduced operating cost, and the minimization of the emissions of NOX, CO2, SO2, and organic PICs. In some NOX control technologies, CO generation is a counteractive result of the poor combustion practice used to deliberately generate the free radicals that subsequently reduce NOX emissions. In these systems, excess CO sometimes must be subsequently oxidized to CO2 to reduce emissions of CO. Excess air (increase). To provide for maximum thermal efficiency, the volumetric concentration of oxygen in the flue gas at the feed end of a rotary kiln and/or the exit of the preheater tower normally are held as close as possible to 1%. Because of site-specific conditions, this oxygen concentration may be insufficient to allow for complete combustion, and CO may be generated at the combustion site. A slight increase in the amount of air passing through the kiln system is often sufficient to reduce the excess CO emissions. An increase in oxygen at the combustion site tends to increase thermal and/or fuel NOX. Additional fuel is required to heat the excess air to combustion temperatures and results in a slight increase in CO2 emissions. The excess air would tend to reduce emissions of SO2 and organic PICs.

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Raw material substitution. Some cement raw materials contain carbonaceous components that are only partially oxidized to CO in the low-temperature regions of the pyroprocess. These situations also may present excessive emissions of organic pollutants. Depending on local availability and costs, replacement of the offending raw material by selective purchasing, selective quarrying or judicious blending may be an effective technology to reduce emissions of CO and/or organic material. The replacement of any raw material should be evaluated for its effect on the process and pollutants of concern. Pyroprocessing system design. Because the emission of CO from unburned fuel represents an economic loss, most cement pyroprocessing systems are designed to ensure the complete combustion of fuels. In those situations where CO generation occurs simultaneously with the deliberate generation of free radicals used as reducing agents to minimize NOX emissions, the process normally is designed to oxidize residual CO to CO2 once the NOX reduction has been accomplished. Each vendor of cement kiln systems has several proprietary designs intended to minimize CO emissions while accomplishing other process and pollution abatement objectives. For example, in a low-NOX calciner, the fuel and tertiary air are introduced appropriately to the vessel to minimize residual CO. In staged combustion, an oxidizing zone sequentially follows a combustion zone that operates in an oxygen-deficient environment. Mixing air fan. High-pressure air in the range of a 2-10% replacement of the primary combustion air can be injected through the shell of the rotary kiln into the calcining zone to provide additional oxygen to the post-combustion flue gas to meet stoichiometric requirements and the kinetic energy necessary for the adequate mixing of flue gas within the kiln. To reduce CO emissions, this technology has an effective synergy with mid-kiln firing of solid fuel, e.g., worn passenger car tires. In a limited number of applications of mixing air fans to a rotary kiln, simultaneous reductions in the emissions of SO2, THC, and NOX have been shown. Regenerative thermal oxidizer. The most thermally efficient of the tailpipe thermal oxidizers is an RTO. As applied to a cement kiln, a RTO consists of several modules, each of which treat an aliquot of the post-PMCD flue gas by reheating it to about 870oC (1600oF) with an open flame and sufficient oxygen to oxidize CO, hydrocarbons, and/or odor-causing constituents. To minimize collateral pollution, a clean fuel, e.g., natural gas, has been the usual choice for use in the RTO technology. The heat from the treated flue gas is captured in one of two porous heat sinks in each module. The untreated flue gas is passed through a hot heat sink to recover heat prior to subsequent thermal oxidation. Upon dissipation of the heat in the initial module, a system of valves quickly reverses the roles of the heat sinks. The process repeats itself through alternative heating and cooling of the heat sinks. The application of an RTO to a cement kiln system appears to require the consideration of additional pollution abatement technologies. The operating temperature of the RTO strongly encourages the conversion of SO2 in the flue gas to SO3. So that SO3 generation is minimized, a common approach is to apply a wet limestone scrubber ahead of the RTO to remove as much SO2 as possible from the flue gas. The wet scrubber also could be expected to remove NH3, a component of many detached plumes, from the flue gas. The spent reagent from the scrubber must be disposed of or fully oxidized to calcium sulfate for use in the finish mill of the cement plant. If necessary, a wet ESP can be applied to the flue gas following the RTO in the gas flow

43

path to further reduce SO3 emissions. The use of a wet scrubber requires even more energy to reheat the flue gas and introduces sufficient humidity to the RTO to require materials of construction that resist aggressive corrosion at temperatures below the acid dew point. An alternative approach would be to use one or more of the pre-PMCD SO2 reduction technologies suitable for cement kiln systems to eliminate the need for the wet scrubber. The combustion of additional fuel in the RTO will result in additional emissions of CO2 and NOX. At the operating temperatures of an RTO, D/Fs in the flue gas would be subject to destruction. Potential control technologies. Thermal oxidizer. Thermal oxidation would involve the reheating of the flue gas to temperatures of 760870oC (14001598oF) in the presence of sufficient oxygen to achieve complete destruction of any CO present in the flue gas. Residual THCs also would be destroyed. Because of its inherent inefficiency, thermal oxidization is seldom applied as a tailpipe technology on a large-scale process such as a cement kiln system. To derive benefit from the additional heat input required by thermal oxidization, an application of thermal oxidization in the gas flow path prior to the raw mill in an in-line kiln/raw mill system is conceptually possible. Because of the additional consumption of fuel, increases in the emissions of CO2 and NOX are unavoidable when compared to the pyroprocess without application of thermal oxidization. At the operating temperatures of an RTO, D/Fs in the flue gas also would be subject to destruction. Recuperative thermal oxidization. In the application of recuperative thermal oxidization, the thermal efficiency of thermal oxidization is improved through the use of a countercurrent gas-to-gas heat exchanger in which heat from the treated flue gas is transferred or recirculated to the untreated flue gas. Recuperative thermal oxidization has the additional potential to reduce THC concentrations in the flue gas and would result in additional emissions of NOX and CO2 because of the additional fuel combustion that is required to raise the flue gas to an effective temperature. At the operating temperatures of an RTO, D/Fs in the flue gas would be subject to destruction. Recuperative thermal oxidization is less thermally efficient than an RTO. Catalytic oxidization. Various catalysts could be used to replace or enhance thermal oxidation or recuperative thermal oxidization by allowing the destruction of CO at a lower temperature, i.e., 310370oC (590698oF). Typically, these catalysts would be contained on a substrate in the form of a grid in the flue gas stream. This technology is currently applied on a much smaller scale than would be required for a cement kiln system. The typical problems involving the blinding and fouling of catalysts by PM, SO2, and chlorine would be experienced in the application of this technology. Because of the additional consumption of fuel, increases in the emissions of CO2 and NOX are unavoidable when compared to a pyroprocess without application of catalytic oxidation. Oxygen enrichment. This technology could reduce generation of CO by improving combustion efficiency in the rotary kiln or calciner. The use of LOX in the high-temperature burning zone tends to increase the short-term generation of thermal and fuel NOX, and to decrease the generation of SO2 and organic PICs. The use of LOX in the calciner would tend to increase the generation of fuel NOX and to reduce the generation of organic PICs.

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Control of Carbon Dioxide

Table 7. Carbon Dioxide Control Technologies. Control technologies Potential effects Synergetic Existing control technologies Improved thermal efficiency Clinker substitution Improved electrical efficiency Raw material substitution Mineralizers Electricity generation from waste heat NOX Project specific Reduction in all gaseous pollutants per ton of cement produced Reduction in all gaseous pollutants per ton of cement produced Material specific AG Counteractive

Reduction in all pollutants related to power generation

Potential control technologies Fuel substitution Electricity generation from the sun and wind Fuel specific Reduction in all pollutants related to power generation

Existing control technologies.

Improved thermal efficiency. The reduction in the amount of carbonaceous fuel burned in a cement kiln system through improved thermal efficiency has a direct relationship to the reduction in emissions of CO2. For existing kiln systems, improvements in thermal efficiency are accomplished primarily through process and process control improvements. Maintenance of components of a kiln system that affect thermal efficiency, e.g., chains and seals, contribute to the maximization of the thermal efficiency of a given kiln system. Complete replacement of a kiln system with a more thermally efficient kiln system achieves a measurable reduction in CO2 emissions per ton of clinker. However, replacement kiln systems tend to have a higher production rate than the unit that was replaced so the total, site-specific emissions of CO2 may not decrease. Each project that improves thermal efficiency should be evaluated for its effect on all pollutants of concern, e.g., the replacement of a wet kiln with a precalciner kiln may result in a significant increase in the emissions of SO2 simply because of the roasting of sulfide sulfur in the preheater tower. Some of the pollution abatement technologies listed in this paper, e.g., a RTO, measurably decrease the thermal efficiency of a cement plant. The increase in emissions of CO2 and other pollutants of concern should be considered in evaluating the environmental effects of any pollution abatement technology. Clinker substitution. The substitution (blending) of other cementitious materials for clinker in the cement matrix reduces the amount of CO2 generated per ton of cement produced and/or used. The blending can occur at the cement plant through intergrinding of the cementitious materials in the finish mill or at the location of the end user, e.g., a ready mixed concrete producer. In the end, the lower CO2 emissions attributed to a specific structure or project are the same regardless of where the clinker substitution or blending takes place. Some substitute

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materials, e.g., power plant fly ash and blast furnace slag, have continuing and independent emissions of CO2 associated with their generation regardless of their use in blended cement. Other than electrical power required for grinding, these materials do not contribute to CO2 emissions during the manufacture of blended cement. Other blended materials, e.g., a manufactured pozzolan, have lower CO2 emissions associated with their manufacture than cement clinker. The emissions of CO2 resulting from the manufacture of these products are an integral part of the manufacture of blended cement. A reduction in the clinker content of blended cement represents a reduction in all gaseous pollutants of concern per ton of cementitious product. Improved electrical efficiency. In most cases, a reduction in the amount of electricity used to produce a ton of cement indirectly results in lower emissions of CO2 from fossil fuel fired power plants. Exceptions would be those few cement plants that produce a portion of their requirements for electrical energy through the use of waste heat boilers and those plants that obtain their electrical power from nuclear or hydroelectric sources. Many of the pollution abatement technologies listed in this paper measurably decrease the electrical efficiency of a cement plant, e.g., larger fans using more electrical power are required to overcome pressure drop across equipment or to move a larger volume of flue gas. The increase in emissions of CO2 and other pollutants at the power plant should be considered in evaluating the environmental effects of any pollution abatement technology. Raw material substitution. Raw material substitution can be marginally effective in reducing CO2 emissions from cement pyroprocesses. Through control of the chemistry of the raw material mix, the clinkering temperature can be lowered slightly thereby requiring marginally less carbonaceous fuel to complete the desired reactions. A change in raw materials is often necessary to significantly alter the raw mix chemistry. Any change in raw materials should be evaluated for its effect on the process and the emission of other pollutants of concern. Calcareous materials, e.g., blast furnace slag, that do not contain carbonates can be used as a substitute for limestone in the raw material mix. Because calcination is the most energy intensive reaction in clinker production, the elimination of a portion of the calcination requirement also reduces carbonaceous fuel consumption. Because of the small and geographically concentrated supplies of suitable calcareous slag, this technology has limited but effective applicability. Other materials with limited availability, e.g., lime kiln dust, might be substituted for a portion of the calcium carbonate source. Because cement plants are normally located at or near their sources of raw materials, there are often critical economic limitations to the practicability of substituting raw materials through selective purchasing, selective quarrying or judicious blending to produce an easier burning mix. The consistent and long-term availability of carbonate-free calcareous materials and their cost-effectiveness also must be evaluated when their use is considered. Mineralizers. When added to the raw material mix, certain chemicals, e.g., calcium fluoride, are known to reduce significantly the clinkering temperature and the carbonaceous fuel required to sustain the pyroprocess. Mineralizers seldom are used because the pyroprocess becomes much more difficult to control and catastrophic process failures, e.g., molten material discharges from the kiln, are possible. The generation and emission of AGs, e.g., HF, or other HAPs is a

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likely possibility. Each potential mineralizer should be evaluated for its effect on the process and the emission of pollutants of concern. Electricity generation from waste heat. In the past, the wet and long dry kiln systems lost a significant portion of their thermal energy input due to the discharge of high-temperature flue gas. Because it was economically attractive at the time, this thermal energy was converted to electrical energy in waste heat boilers. As the existing pyroprocessing systems became more energy efficient through process and process control improvements or were replaced by the more efficient preheater and precalciner kiln systems, the waste heat available for electricity generation was reduced to the point of technical impossibility or unattractive economic returns. There are very few cement plants in the United States that still have waste heat boilers. These systems operate intermittently depending on the local cost of electricity. New cogeneration systems that utilize low boiling temperature liquids are becoming available and may have application in the cement industry on kilns and clinker coolers.

Potential control technologies.

Fuel substitution. The substitution of a hydrocarbon fuel, e.g., natural gas or oil, for coal and/or petroleum coke will result in lower overall emissions of CO2 for a given kiln system. Prior to the energy crises of the 1970s, most cement kilns were fired with natural gas or oil. In response to government guidance, the cement industry switched to solid fossil fuel as its primary source of thermal energy. Currently, natural gas and oil are often prohibitively expensive and in limited supply. These fuels are unavailable at some cement plant locations. Because there are better uses for natural gas and oil, e.g., residential space heating, this technology is not one that will be used by the cement industry for the reduction of CO2 emissions. Although a well-known and effective technology for CO2 reduction, fuel substitution is not a practical alternative. Electricity generation from the sun and wind. Some rural cement plants are well located to utilize these technologies when they become more highly developed and commercially available. The substitution of electrical power from the sun or wind for electrical power from fossil fuels will reduce the emissions of CO2 and all other pollutants associated with fossil fuel combustion.

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Control of Ammonia
Table 8. Ammonia Control Technologies. Control technologies Potential effects Synergetic Potential control technologies Raw material substitution Tailpipe wet scrubber SO2, THC Material specific Wastewater Counteractive

Potential control strategies.

Raw material substitution. The involvement of NH3 in the formation of detached plumes and as a precursor to regional haze formation is a concern. If a component of the raw material mix contains nitrogenous components that are converted to or liberated as NH3 in the pyroprocess, the raw material could be replaced if a suitable, economically-viable substitute is locally available through selective purchasing, selective quarrying or judicious blending. At present, the potential for NH3 generation because of a raw material may only be determined by trial and error in the process. Therefore, it may be more productive to consider control of other precursors of a detached plume, e.g., SO2, before a change in raw material is attempted. Any raw material substitution for the purpose of pollution control should be evaluated for its effect on the process and the emission of other pollutants of concern. In one plant familiar to the author, NH3 originating in the raw material mix is thought to contribute to unusually low NOX emissions through a serendipitous reaction similar to SNCR. Tailpipe wet scrubber. NH3 is highly soluble in water so a water spray tower should suffice to scrub NH3 from the flue gas should NH3 abatement become necessary. The spray tower also would remove some soluble SO2 and residual organic compounds from the flue gas. It is likely that the wastewater would have to be treated prior to discharge.

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Control of Acid Gases

Table 9. Acid Gas Control Technologies. Control technologies Potential effects Synergetic Existing control technologies Decrease SO2 generation Raw material substitution SO2 Material specific Potential Control Technologies Wet electrostatic precipitator Tailpipe wet scrubber Tailpipe dry scrubber Fabric filter absorption Tailpipe dry bicarbonate injection Temperature control THC, SO2, NOX, PM, NH3, D/F, detached plume SO2, NH3, THC SO2, THC SO2 SO2, D/F, detached plume SO2, NH3, THC, D/F, detached plume Waste disposal Water/waste disposal PM, Acid mist CO2, NOX Counteractive

Existing control technologies.

Decrease SO2 generation. The precursor to the emissions of sulfuric acid and SO3 is SO2. Any of the technologies that can reduce the generation of SO2 or improve its capture in the process would tend to lower the emissions of sulfuric acid and/or SO3. Without the use of additional pollution prevention steps, some tailpipe technologies, e.g., a RTO, tend to increase the emissions of SO3. Wet limestone scrubbers have been known to emit sulfuric acid mist. Raw material substitution. Appropriate raw material substitution through selective purchasing, selective quarrying or judicious blending is one of the technologies that can decrease SO2 generation and the resulting formation of sulfurous acid or sulfuric acid mist. Although the mechanism of HCl generation is not fully understood, raw material substitution could be helpful in reducing HCl emissions. During limited tests at one plant, varying the input of chlorine in the fuel did not affect emissions of HCl. However, at another plant, a change to a low-chlorine limestone from a high-chlorine marine deposit of aragonite eliminated a detached plume that had been determined to result from the condensation of ammonium chloride in the atmosphere. One precursor to the formation of ammonium chloride was thought to be HCl. At present, the effect of raw material substitution on HCl generation can only be determined by site-specific trial and error. Any raw material substitution for the purpose of pollution control should be evaluated for its effect on the process and the emission of other pollutants of concern. Because cement plants are normally located at or near their sources of raw materials, there could be critical economic limitations to the practicability of substituting raw materials to eliminate acid gas emissions.

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Potential control technologies.

Wet electrostatic precipitator. Several vendors supply proprietary wet ESPs. These devices are similar in operating principle to a dry ESP except that they operate at a temperature well below the boiling point of water, and water is used to flush the pollutants from the collecting plates. Wet ESPs frequently are used to collect acid gases and mists from a variety of sources. Vendors of wet ESPs claim that they are effective in the collection of submicron PM, condensed organic material, volatile metals, NH3 and D/F. In some applications, reductions in the emission of SO2 and NOX also are claimed. If applied to a cement kiln system, there must not be any cement minerals in the flue gas. Otherwise, there will be a buildup of hydrated cement in the wet ESP that will cause the ESP to fail and require manual cleaning. A process location following a wet kiln, a long-dry kiln, or an alkali bypass would not be feasible. A wet ESP should function following a preheater or an in-line raw mill. Tailpipe wet scrubber. Because of the solubility of the acid gases of concern, their concentration in the flue gas could be reduced with a water scrubber located after the main and/or bypass PMCD. The low-pH water generated in a wet scrubber would require neutralization and/or other treatment prior to discharge. Wet scrubbers using hydrated lime or limestone as the scrubbing reagent are known to emit acid mists and might be poor candidates to provide primary control of acid gases. In addition, there would be potential problems with waste disposal and/or high pH effluent resulting from the operation of a reagent-based wet scrubber. A wet scrubber, with or without a reagent, also could remove some SO2, NH3, and condensable organic pollutants from the flue gas. Tailpipe dry scrubber. A tailpipe dry scrubber at a cement plant would use hydrated lime or limestone slurry as the scrubbing reagent for acid gases. The flue gas would have to be reheated with a liquid or gaseous fuel to accomplish the required evaporation of water from the reagent before its collection in a fabric filter. The increased fuel consumption would result in additional emissions of CO2 and NOX. The dry scrubber also would remove some SO2 and condensable organic material from the flue gas. Depending on the captured pollutants, spent reagent could be used as a raw material in the cement plant rather than disposed. Fabric filter absorption. Under certain conditions, the alkaline material collected in the main or bypass fabric filters in a cement kiln system could absorb or react with the acid gases in the flue gas. A more active reagent such as calcium hydroxide could be added to the flue gas stream ahead of the fabric filter to collect acid gases through the process of adsorption. As applied in a cement kiln system, this technology would provide only a marginal reduction, if any, in acid gas and SO2 emissions with poor reagent utilization. Tailpipe dry bicarbonate injection. The largest supplier of sodium bicarbonate in the world, Church and Dwight Co., Inc., claims the removal of AGs from flue gas using dry sodium bicarbonate as the sorbent reagent. The applicable temperature of the technology is said to be 149-538oC (300-1000oF), a temperature that should make the technology theoretically suitable as a tailpipe technology for a cement kiln system. Because the sodium generally could not be returned to the pyroprocess for reasons of product quality, the injection of the bicarbonate often would have to occur after the main PMCD, and a final PMCD would be required to collect the

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reaction products and unreacted reagent for subsequent disposal in an appropriate landfill that might not be available on site. Through the use of a proprietary 90/10 blend of sodium bicarbonate and PAC, the simultaneous removal of AGs, D/F and heavy metals from the flue gas also is claimed (Church & Dwight, 1999). Temperature control. If the flue gas is cooled below the acid dew point, the acid gas will condense on cool surfaces or as droplets in the gas stream. The condensation would be accomplished most likely through the introduction of ambient air or water to the flue gas stream. The condensed acids must be collected as liquids or on a sorbent, neutralized, and disposed. A portion of other temperature and/or moisture sensitive pollutants, e.g., SO2, NH3, THC, and D/F, would be condensed also. The materials of construction used for equipment operating below the acid dew point must be highly corrosion resistant or they will not survive the attack of the condensed acids.

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Control of Dioxins and Furans

Table 10. Dioxin and Furan Control Technologies. Control technologies Potential effects Synergetic Existing control technologies PMCD inlet temperature control Reduced residence time at temperature Potential control technologies Raw material substitution Wet electrostatic precipitator Catalytic filtration (fabric filter bags) Granular activated carbon adsorption Powdered activated carbon adsorption Material specific THC, SO2, NOX, PM, NH3, AG, Detached plume PM NOX, SO2, organics, metals NOX, SO2, organics, metals Waste disposal, high reagent consumption D/F, Waste disposal, high reagent consumption Material specific Counteractive

Existing control technologies.

Particulate matter control device inlet temperature control. USEPA has determined that D/F emissions in cement kiln systems are related directly to the inlet temperature of the main and bypass PMCDs serving the system. The regulations in 40 CFR 63.1343 essentially contain a maximum target temperature of 204oC (400oF) that will provide for minimum emissions of D/F. In many pyroprocessing systems, e.g., those with an in-line kiln/raw mill, this temperature is met during normal operation. In other systems, it has been necessary to use water sprays or ambient air to cool the flue gas prior to the PMCD inlet. In a new or reconstructed kiln system, the process can be designed to meet this temperature limit without approaching the acid dew point in the PMCD. Reduced residence time at temperature. There is nothing directly related to the formation of D/F that is unique to a PMCD. The formation of D/F appears to be dependent on the time that flue gas remains in the critical temperature window. In most kiln systems, the point of lowest linear velocity of the flue gas is in the PMCD. However, there could be other locations in the process that meet the time/temperature relationship. Should this be the case, the flue gas velocity and/or temperature could be altered to provide for the process conditions necessary to minimize D/F formation.

Potential control technologies.

Raw material substitution. There are a few instances where D/Fs have been identified in native raw materials or in by-product materials used in a cement kiln raw mix that were associated with unexpected increases in D/F emissions from the kiln (Schreiber, 1995; Richards, 2003). If necessary, the involved raw material could be replaced to lower the D/F emissions. 52

Selective purchasing, selective quarrying or judicious blending of available raw materials could be used to accomplish the replacement. Whenever a raw material is changed, there may be unintended effects on the process and the resulting pollutants. Because cement plants normally are located at or near their sources of raw materials, there are often critical economic limitations to the practicability of substituting raw materials to reduce the input D/Fs. Wet electrostatic precipitator. Several vendors supply proprietary wet ESPs. These devices are similar in operating principle to a dry ESP except that they operate at a temperature well below the boiling point of water, and water is used to flush the pollutants from the collecting plates. It is claimed that wet ESPs collect D/F from a flue gas stream. Although wet ESPs are perhaps best known for the collection of acid mists, vendors claim that they are also effective in the collection of submicron PM, condensed organic material, volatile metals, and NH3. In some applications, reductions in the emission of SO2 and NOX also are claimed. Catalytic filtration (fabric filter bags). Proprietary catalyst impregnated fabric filter bags have been used widely to reduce emissions of D/F in the flue gas from municipal waste incinerators (Gore, 1999). This technology could be appropriate for application to cement kiln systems that are not able to adequately reduce the D/F concentration in the flue gas through PMCD temperature control. The fabric filter bags are composed of a catalytic felt substrate of polytetrafluoroethylene (PTFE) to which a membrane of PTFE has been laminated. These filter bags are suitable for any application on cement kiln systems in which standard PTFE bags would be used including main and bypass PMCDs. PTFE fabric filter bags have been shown to provide outstanding collection of PM from cement kiln flue gas when compared to traditional filter cloth. Granular activated carbon adsorption. GAC is made from many carbon-containing materials including bituminous coal. For large-scale applications in the United States, e.g., cement kilns, the raw materials of choice would be wood, bituminous coal, or lignite. After carbonization, GAC is processed to increase the internal surface contact area through the creation of pores and channels in each granule. GAC would be contained in thick beds inside vessels through which flue gas would be passed. The nonselective absorption on and within GAC of D/F, SO2, NOX, metals, and organic compounds that are contained in cement kiln flue gas could result in rapid depletion of the adsorbent and breakthrough of D/Fs. Depending on economic factors and the adsorbed constituents, GAC could be regenerated on site or sent to a specialized offsite location for regeneration. In some cases, the spent GAC could be classified as a hazardous waste. The collected constituents that are removed from spent GAC must be collected, destroyed, recycled, or disposed. Depending on the adsorbed constituents, spent GAC could be burned as supplemental fuel in a cement kiln. The generation of CO2 and other pollutants of concern during the manufacture of GAC should be taken into account when considering the use of GAC. Powdered activated carbon adsorption. Essentially the same processes produce PAC and GAC except that with PAC the adsorbent is in the form of a very fine powder with high surface area. Rather than being placed in adsorbing beds, PAC would be injected into and intimately mixed with the flue gas. In 40 CFR 63, subpart LLL, the EPA has listed PAC injection as a control technology for D/Fs. PAC would adsorb the same constituents as GAC but might not be fully saturated in the available contact time, i.e., poor sorbent utilization. If PAC were injected

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ahead of the main or bypass PMCD, then the used PAC would become part of the raw material stream, or the disposed or recirculated CKD. If used PAC were in the raw material or recirculated CKD, organic compounds and other volatile constituents adsorbed by the PAC would contribute to the building of a circulating load within the pyroprocess. At some point in time, the circulating load would reach equilibrium and emissions of the pollutants of concern would resume at the rate of generation by or introduction into the process. The inclusion of used PAC in the CKD would avoid the problem of volatile pollutant recirculation, but the disposal or beneficial use of the CKD could be compromised because of the PAC itself and/or the adsorbed pollutants in the PAC. If PAC were injected into the flue gas after the main PMCD, the used PAC would be collected in a tailpipe PMCD and disposed. It is possible that the used PAC would be classified as a hazardous waste because of adsorbed constituents of concern. Depending on the adsorbed constituents, the used PAC could be burned as supplemental fuel in the cement kiln. If the used PAC is free of PM from the cement pyroprocess, potentially it could be regenerated and reused. In some applications, it has been observed that the use of PAC actually contributes to the formation of D/F. The generation of CO2 and other pollutants of concern during manufacture of PAC should be taken into account when considering the use of PAC.

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CONCLUSIONS
Because of the variations in raw materials, fuels, and processes, cement pyroprocessing systems are not amenable to one-size-fits all strategies for control of the generation and emission of gaseous pollutants of concern. There are several existing and potential pollution control technologies that have applicability to cement kilns. Some of these technologies have synergetic and counteractive interactions with other technologies and with pollutants they are not intended to control. Technologies that take advantage of the inherent characteristics of the pyroprocesses to which they are applied tend to be effective, reasonably energy-efficient, and cost-effective. Many of these technologies can be and are simultaneously applied to cement kiln systems with positive results. While environmentally effective, tailpipe technologies tend be mutually exclusive, to require additional electrical and/or thermal energy, and to burden a cement plant with capital, operating, maintenance, and disposal costs that could put continued operation of the plant at risk. Each cement pyroprocess has a unique effect on the environment and often has a site-specific need for pollution control beyond that afforded by the basic process. Before application to a new or existing kiln system, a pollution abatement technology must be evaluated for its potential for pollution reduction, and its effects on the process and potential costs. Most pollution control strategies must accommodate compromise in the selection of pollution abatement technologies that result in the maximum overall benefit to the environment with minimum negative consequences.

ACKNOWLEDGEMENTS
The research reported in this paper (PCA R&D Serial No. 2728) was conducted by Trinity Consultants with the sponsorship of the Portland Cement Association (PCA Project Index No. 02-12). The contents of this report reflect the views of the author, who is responsible for the facts and accuracy of the data presented. The contents do not necessarily reflect the views of the Portland Cement Association.

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