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Cement kilns are mechanical, industrial furnace used for the pyroprocessing stage of manufacture of Portland cement and other types of hydraulic cement. The kilns use high heat to cook calcium carbonate with silicon dioxide-bearing minerals to create the more reactive mixture of , called Cement clinker, which is ground into a fine powder that is the main component of cements and Concrete.
Kilns are relatively distributed technologies all over the world: over a billion tonnes of cement are made per year, and cement kiln capacity defines the capacity of the cement plants. The kilns is an integrated part of the cement plant, connected by a number of ancillary pieces of equipment, used to engineer an ideal flow of cement to the rest of the system. Improvement to kiln systems and ancillary equipment, such as heat recovery, can improve the efficiency kilns and reduce the cost of overall operation of a cement plan.
Emissions from cement kilns are a major source of greenhouse gas emissions, accounting for around 2.5% of non-natural carbon emissions worldwide. The emissions come from two sources: the fuel and the waste CO2 created from heating the silicate rocks. Conventional cement kilns burn Fossil fuel or alternative fuels like tire waste, agricultural waste or other wastes, as a form of waste valorization. Because of the need to reduce emissions to mitigate climate change, multiple companies are investing in alternative fuel sources, including investigations of hydrogen or electricity based heating. Other mitigation approaches, include capturing carbon dioxide from the process at the exhaust stage of the kiln, and reducing use of clinker in final mix of concretes.
Kilns also produce other toxic emissions, such as particulates, Sulfer Dioxide, Nitrous dioxide and other industrial emissions. If not mitigated correctly at the emissions pipe, surrounding communities can have Air pollution.
Around 1885, experiments began on design of continuous kilns. One design was the shaft kiln, similar in design to a blast furnace. Rawmix in the form of lumps and fuel were continuously added at the top, and clinker was continually withdrawn at the bottom. Air was blown through under pressure from the base to combust the fuel. The shaft kiln had a brief period of use before it was eclipsed by the rotary kiln, but it had a limited renaissance from 1970 onward in China and elsewhere, when it was used for small-scale, low-tech plants in rural areas away from transport routes. Several thousand such kilns were constructed in China. A typical shaft kiln produces 100-200 tonnes per day.
From 1885, trials began on the development of the rotary kiln, which today accounts for more than 95% of world production.
The earliest successful rotary kilns were developed in Pennsylvania around 1890, based on a design by Frederick Ransome, and were about 1.5 m in diameter and 15 m in length. Such a kiln made about 20 tonnes of clinker per day. The fuel, initially, was oil, which was readily available in Pennsylvania at the time. It was particularly easy to get a good flame with this fuel. Within the next 10 years, the technique of firing by blowing in pulverized coal was developed, allowing the use of the cheapest available fuel. By 1905, the largest kilns were 2.7 x 60 m in size, and made 190 tonnes per day. At that date, after only 15 years of development, rotary kilns accounted for half of world production. Since then, the capacity of kilns has increased steadily, and the largest kilns today produce around 10,000 tonnes per day. In contrast to static kilns, the material passes through quickly: it takes from 3 hours (in some old wet process kilns) to as little as 10 minutes (in short precalciner kilns). Rotary kilns run 24 hours a day, and are typically stopped only for a few days once or twice a year for essential maintenance. One of the main maintenance works on rotary kilns is tyre and roller surface machining and grinding works which can be done while the kiln works in full operation at speeds up to 3.5 rpm. This is an important discipline, because heating up and cooling down are long, wasteful, and damaging processes. Uninterrupted runs as long as 18 months have been achieved.
The wet process suffered the obvious disadvantage that, when the slurry was introduced into the kiln, a large amount of extra fuel was used in evaporating the water. Furthermore, a larger kiln was needed for a given clinker output, because much of the kiln's length was committed to the drying process. On the other hand, the wet process had a number of advantages. Wet grinding of hard minerals is usually much more efficient than dry grinding. When slurry is dried in the kiln, it forms a granular crumble that is ideal for subsequent heating in the kiln. In the dry process, it is very difficult to keep the fine powder rawmix in the kiln, because the fast-flowing combustion gases tend to blow it back out again. It became a practice to spray water into dry kilns in order to "damp down" the dry mix, and thus, for many years there was little difference in efficiency between the two processes, and the overwhelming majority of kilns used the wet process. By 1950, a typical large, wet process kiln, fitted with drying-zone heat exchangers, was 3.3 x 120 m in size, made 680 tonnes per day, and used about 0.25–0.30 tonnes of coal fuel for every tonne of clinker produced. Before the energy crisis of the 1970s put an end to new wet-process installations, kilns as large as 5.8 x 225 m in size were making 3000 tonnes per day.
An interesting footnote on the wet process history is that some manufacturers have in fact made very old wet process facilities profitable through the waste-to-energy. Plants that burn waste fuels enjoy a negative fuel cost (they are paid by industries needing to dispose of materials that have energy content and can be safely disposed of in the cement kiln thanks to its high temperatures and longer retention times). As a result, the inefficiency of the wet process is an advantage—to the manufacturer. By locating waste burning operations at older wet process locations, higher fuel consumption actually equates to higher profits for the manufacturer, although it produces correspondingly greater emission of CO2. Manufacturers who think such emissions should be reduced are abandoning the use of wet process.
The number of cyclones stages used in practice varies from 1 to 6. Energy, in the form of fan-power, is required to draw the gases through the string of cyclones, and at a string of 6 cyclones, the cost of the added fan-power needed for an extra cyclone exceeds the efficiency advantage gained. It is normal to use the warm exhaust gas to dry the raw materials in the rawmill, and if the raw materials are wet, hot gas from a less efficient preheater is desirable. For this reason, the most commonly encountered suspension preheaters have 4 cyclones. The hot feed that leaves the base of the preheater string is typically 20% calcined, so the kiln has less subsequent processing to do, and can therefore achieve a higher specific output. Typical large systems installed in the early 1970s had cyclones 6 m in diameter, a rotary kiln of 5 x 75 m, making 2500 tonnes per day, using about 0.11-0.12 tonnes of coal fuel for every tonne of clinker produced.
A penalty paid for the efficiency of suspension preheaters is their tendency to block up. Salts, such as the sulfate and chloride of sodium and potassium, tend to evaporate in the burning zone of the kiln. They are carried back in vapor form, and re-condense when a sufficiently low temperature is encountered. Because these salts re-circulate back into the rawmix and re-enter the burning zone, a recirculation cycle establishes itself. A kiln with 0.1% chloride in the rawmix and clinker may have 5% chloride in the mid-kiln material. Condensation usually occurs in the preheater, and a sticky deposit of liquid salts glues dusty rawmix into a hard deposit, typically on surfaces against which the gas-flow is impacting. This can choke the preheater to the point that air-flow can no longer be maintained in the kiln. It then becomes necessary to manually break the build-up away. Modern installations often have automatic devices installed at vulnerable points to knock out build-up regularly. An alternative approach is to "bleed off" some of the kiln exhaust at the kiln inlet where the salts are still in the vapor phase, and remove and discard the solids in this. This is usually termed an "alkali bleed" and it breaks the recirculation cycle. It can also be of advantage for cement quality reasons, since it reduces the alkali content of the clinker. The alkali content is a critical property of cement. Indeed, cement with a too high alkali content can cause a harmful alkali–silica reaction (ASR) in concrete made with aggregates containing reactive amorphous silica. Hygroscopic and swelling sodium silicate is formed inside the reactive aggregates which develop characteristic internal fissures. This expansive chemical reaction occurring in the concrete matrix generate high tensile stress in concrete and creates cracks that can ruin a concrete structure. However, hot gas is run to waste so the process is inefficient and increases kiln fuel consumption.
The ultimate development is the "air-separate" precalciner, in which the hot combustion air for the calciner arrives in a duct directly from the cooler, bypassing the kiln. Typically, 60-75% of the fuel is burned in the precalciner. In these systems, the feed entering the rotary kiln is 100% calcined. The kiln has only to raise the feed to sintering temperature. In theory the maximum efficiency would be achieved if all the fuel were burned in the preheater, but the sintering operation involves partial melting and nodulization to make clinker, and the rolling action of the rotary kiln remains the most efficient way of doing this. Large modern installations typically have two parallel strings of 4 or 5 cyclones, with one attached to the kiln and the other attached to the precalciner chamber. A rotary kiln of 6 x 100 m makes 8,000–10,000 tonnes per day, using about 0.10-0.11 tonnes of coal fuel for every tonne of clinker produced. The kiln is dwarfed by the massive preheater tower and cooler in these installations. Such a kiln produces 3 million tonnes of clinker per year, and consumes 300,000 tonnes of coal. A diameter of 6 m appears to be the limit of size of rotary kilns, because the flexibility of the steel shell becomes unmanageable at or above this size, and the fire brick lining tends to fail when the kiln flexes.
A particular advantage of the air-separate precalciner is that a large proportion, or even 100%, of the alkali-laden kiln exhaust gas can be taken off as alkali bleed (see above). Because this accounts for only 40% of the system heat input, it can be done with lower heat wastage than in a simple suspension preheater bleed. Because of this, air-separate precalciners are now always prescribed when only high-alkali raw materials are available at a cement plant.
The accompanying figures show the movement towards the use of the more efficient processes in North America (for which data is readily available). But the average output per kiln in, for example, Thailand is twice that in North America.
(as alite is responsible for the early strength development in cement setting and hardening, the highest possible content of the clinker in alite is desirable)
and, (2) because they do not rotate, hot air can be ducted out of them for use in fuel drying, or for use as precalciner combustion air. The latter advantage means that they have become the only type used in modern systems .
In indirect firing, the fuel is ground by an intermittently run mill, and the fine product is stored in a silo of sufficient size to supply the kiln though fuel mill stoppage periods. The fine fuel is metered out of the silo at a controlled rate and blown into the kiln. This method is now favoured for precalciner systems, because both the kiln and the precalciner can be fed with fuel from the same system. Special techniques are required to store the fine fuel safely, and coals with high coal assay are normally milled in an inert atmosphere (e.g. CO2).
Cement kilns are an attractive way of disposing of hazardous materials, because of:
A notable example is the use of scrapped motor-vehicle tires, which are very difficult to dispose of by other means. Whole tires are commonly introduced in the kiln by rolling them into the upper end of a preheater kiln, or by dropping them through a slot midway along a long wet kiln. In either case, the high gas temperatures (1000–1200 °C) cause almost instantaneous, complete and smokeless combustion of the tire. Alternatively, tires are chopped into 5–10 mm chips, in which form they can be injected into a precalciner combustion chamber. The steel and zinc in the tires become chemically incorporated into the clinker, partially replacing iron that must otherwise be fed as raw material.
A high level of monitoring of both the fuel and its combustion products is necessary to maintain safe operation.
08 March 2016
For maximum kiln efficiency, high quality conventional fuels are the best choice. However, burning any fuels, especially hazardous waste materials, can result in toxic emissions. Thus, it is necessary for operators of cement kilns to closely monitor many process variables to ensure emissions are continuously minimized. In the U.S., cement kilns are regulated as a major source of air pollution by the EPA and must meet stringent air pollution control requirements.
Formation of the desired clinker minerals involves heating the rawmix through the temperature stages mentioned above. The finishing transformation that takes place in the hottest part of the kiln, under the flame, is the reaction of belite () with calcium oxide to form alite ():
Also abbreviated in the cement chemist notation (CCN) as:
If the reaction is incomplete, excessive amounts of free calcium oxide remain in the clinker. Regular measurement of the free CaO content is used as a means of tracking the clinker quality. As a parameter in kiln control, free CaO data is somewhat ineffective because, even with fast automated sampling and analysis, the data, when it arrives, may be 10 minutes "out of date", and more immediate data must be used for minute-to-minute control.
Conversion of belite to alite requires partial melting, the resulting liquid being the solvent in which the reaction takes place. The amount of liquid, and hence the speed of the finishing reaction, is related to temperature. To meet the clinker quality objective, the most obvious control is that the clinker should reach a peak temperature such that the finishing reaction takes place to the required degree. A further reason to maintain constant liquid formation in the hot end of the kiln is that the sintering material forms a dam that prevents the cooler upstream feed from flooding out of the kiln. The feed in the calcining zone, because it is a powder evolving carbon dioxide, is extremely fluid. Cooling of the burning zone, and loss of unburned material into the cooler, is called "flushing", and in addition to causing lost production can cause massive damage.
However, for efficient operation, steady conditions need to be maintained throughout the whole kiln system. The feed at each stage must be at a temperature such that it is "ready" for processing in the next stage. To ensure this, the temperature of both feed and gas must be optimized and maintained at every point. The external controls available to achieve this are few:
The independent use of fan speed and fuel rate is constrained by the fact that there must always be sufficient oxygen available to burn the fuel, and in particular, to burn carbon to carbon dioxide. If carbon monoxide is formed, this represents a waste of fuel, and also indicates redox within the kiln which must be avoided at all costs since it causes destruction of the clinker mineral structure. For this reason, the exhaust gas is continually analyzed for oxygen, carbon monoxide, nitric oxide and sulfur dioxide.
The assessment of the clinker peak temperature has always been problematic. Contact temperature measurement is impossible because of the chemically aggressive and abrasive nature of the hot clinker, and optical methods such as infrared pyrometry are difficult because of the dust and fume-laden atmosphere in the burning zone. The traditional method of assessment was to view the bed of clinker and deduce the amount of liquid formation by experience. As more liquid forms, the clinker becomes stickier, and the bed of material climbs higher up the rising side of the kiln. It is usually also possible to assess the length of the zone of liquid formation, beyond which powdery "fresh" feed can be seen. Cameras, with or without infrared measurement capability, are mounted on the kiln hood to facilitate this. On many kilns, the same information can be inferred from the kiln motor power drawn, since sticky feed riding high on the kiln wall increases the eccentric turning load of the kiln. Further information can be obtained from the exhaust gas analyzers. The formation of NO from nitrogen and oxygen takes place only at high temperatures, and so the NO level gives an indication of the combined feed and flame temperature. SO2 is formed by thermal decomposition of calcium sulfate in the clinker, and so also gives an indication of clinker temperature. Modern computer control systems usually make a "calculated" temperature, using contributions from all these information sources, and then set about controlling it.
As an exercise in process control, kiln control is extremely challenging, because of multiple inter-related variables, non-linear responses, and variable process lags. Computer control systems were first tried in the early 1960s, initially with poor results due mainly to poor process measurements. Since 1990, complex high-level supervisory control systems have been standard on new installations. These operate using expert system strategies, that maintain a "just sufficient" burning zone temperature, below which the kiln's operating condition will deteriorate catastrophically, thus requiring rapid-response, "knife-edge" control.
The following descriptions of emissions refer to modern kiln plants based on dry process technology.
Without reduction measures, process-related NOx contents in the exhaust gas of rotary kiln plants would in most cases considerably exceed the specifications of e.g. European legislation for waste burning plants (0.50 g/m3 for new plants and 0.80 g/m3 for existing plants). Reduction measures are aimed at smoothing and optimising plant operation. Technically, staged combustion and SNCR (SNCR) are applied to cope with the emission limit values.
High process temperatures are required to convert the raw material mix to Portland cement clinker. Kiln charge temperatures in the sintering zone of rotary kilns range at around 1450 °C. To reach these, flame temperatures of about 2000 °C are necessary. For reasons of clinker quality the burning process takes place under oxidising conditions, under which the partial oxidation of the molecular nitrogen in the combustion air resulting in the formation of nitrogen monoxide (NO) dominates. This reaction is also called thermal NO formation. At the lower temperatures prevailing in a precalciner, however, thermal NO formation is negligible: here, the nitrogen bound in the fuel can result in the formation of what is known as fuel-related NO. Staged combustion is used to reduce NO: calciner fuel is added with insufficient combustion air. This causes CO to form.
The CO then reduces the NO into molecular nitrogen:
Hot tertiary air is then added to oxidize the remaining CO.
The sulfur input with the fuels is completely converted to SO2 during combustion in the rotary kiln. In the preheater and the kiln, this SO2 reacts to form alkali sulfates, which are bound in the clinker, provided that oxidizing conditions are maintained in the kiln.
The emissions of CO and organically bound carbon during the clinker burning process are caused by the small quantities of organic constituents input via the natural raw materials (remnants of organisms and plants incorporated in the rock in the course of geological history). These are converted during kiln feed preheating and become oxidized to form CO and CO2. In this process, small portions of organic trace gases (total organic carbon) are formed as well. In case of the clinker burning process, the content of CO and organic trace gases in the clean gas therefore may not be directly related to combustion conditions. The amount of released CO2 is about half a ton per ton of clinker.
Under the conditions prevailing in the clinker burning process, non-volatile elements (e.g. arsenic, vanadium, nickel) are completely bound in the clinker.
Elements such as lead and cadmium preferentially react with the excess chlorides and sulfates in the section between the rotary kiln and the preheater, forming volatile compounds. Owing to the large surface area available, these compounds condense on the kiln feed particles at temperatures between 700 °C and 900 °C. In this way, the volatile elements accumulated in the kiln-preheater system are precipitated again in the cyclone preheater, remaining almost completely in the clinker.
Thallium (as the chloride) condenses in the upper zone of the cyclone preheater at temperatures between 450 °C and 500 °C. As a consequence, a cycle can be formed between preheater, raw material drying and exhaust gas purification.
Mercury and its compounds are not precipitated in the kiln and the preheater. They condense on the exhaust gas route due to the cooling of the gas and are partially adsorbed by the raw material particles. This portion is precipitated in the kiln exhaust gas filter.
Owing to trace element behaviour during the clinker burning process and the high precipitation efficiency of the dust collection devices, trace element emission concentrations are on a low overall level.
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