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113-474: Nacala was founded as a little town and developed as a deep waters port and an industrial, agricultural and exporting centre during the last period of the Portuguese rule of the territory which ended in the mid-1970s. Among its major industries were cement , sisal and cashew . Other important employers were the seaport, its small modern hospital, and services (banking, insurance and administration). Nacala

226-554: A chemical reaction between the dry ingredients and water. The chemical reaction results in mineral hydrates that are not very water-soluble. This allows setting in wet conditions or under water and further protects the hardened material from chemical attack. The chemical process for hydraulic cement was found by ancient Romans who used volcanic ash ( pozzolana ) with added lime (calcium oxide). Non-hydraulic cement (less common) does not set in wet conditions or under water. Rather, it sets as it dries and reacts with carbon dioxide in

339-558: A mortar made of sand and roughly burnt gypsum (CaSO 4 · 2H 2 O), which is plaster of Paris, which often contained calcium carbonate (CaCO 3 ), Lime (calcium oxide) was used on Crete and by the Ancient Greeks . There is evidence that the Minoans of Crete used crushed potsherds as an artificial pozzolan for hydraulic cement. Nobody knows who first discovered that a combination of hydrated non-hydraulic lime and

452-417: A chain-like high-temperature steel moving grate, attached to the cold end of the rotary kiln. A dry-powder rawmix is turned into a hard pellets of 10–20 mm diameter in a nodulizing pan, with the addition of 10-15% water. The pellets are loaded onto the moving grate, and the hot combustion gases from the rear of the kiln are passed through the bed of pellets from beneath. This dries and partially calcines

565-408: A controlled bond with masonry blocks. Expansive cements contain, in addition to Portland clinker, expansive clinkers (usually sulfoaluminate clinkers), and are designed to offset the effects of drying shrinkage normally encountered in hydraulic cements. This cement can make concrete for floor slabs (up to 60 m square) without contraction joints. Cement kiln Cement kilns are used for

678-408: A day to fill the kiln, three days to burn off, two days to cool, and a day to unload. Thus, a kiln would produce about 1500 tonnes per year. 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

791-432: A fine powder. This product, made into a mortar with sand, set in 5–15 minutes. The success of "Roman cement" led other manufacturers to develop rival products by burning artificial hydraulic lime cements of clay and chalk . Roman cement quickly became popular but was largely replaced by Portland cement in the 1850s. Apparently unaware of Smeaton's work, the same principle was identified by Frenchman Louis Vicat in

904-432: A form of hydraulic cement, is by far the most common type of cement in general use around the world. This cement is made by heating limestone (calcium carbonate) with other materials (such as clay ) to 1,450 °C (2,640 °F) in a kiln , in a process known as calcination that liberates a molecule of carbon dioxide from the calcium carbonate to form calcium oxide , or quicklime, which then chemically combines with

1017-678: A half-century. Technologies of waste cementation have been developed and deployed at industrial scale in many countries. Cementitious wasteforms require a careful selection and design process adapted to each specific type of waste to satisfy the strict waste acceptance criteria for long-term storage and disposal. Modern development of hydraulic cement began with the start of the Industrial Revolution (around 1800), driven by three main needs: Modern cements are often Portland cement or Portland cement blends, but other cement blends are used in some industrial settings. Portland cement,

1130-787: A market for use in concrete. The use of concrete in construction grew rapidly from 1850 onward, and was soon the dominant use for cements. Thus Portland cement began its predominant role. Isaac Charles Johnson further refined the production of meso-Portland cement (middle stage of development) and claimed he was the real father of Portland cement. Setting time and "early strength" are important characteristics of cements. Hydraulic limes, "natural" cements, and "artificial" cements all rely on their belite (2 CaO · SiO 2 , abbreviated as C 2 S) content for strength development. Belite develops strength slowly. Because they were burned at temperatures below 1,250 °C (2,280 °F), they contained no alite (3 CaO · SiO 2 , abbreviated as C 3 S), which

1243-403: 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

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1356-650: A modern kiln typically amount to 2 tonnes (or 1500 cubic metres at STP ) per tonne of clinker made. The gases carry a large amount of dust—typically 30 grams per cubic metre. Environmental regulations specific to different countries require that this be reduced to (typically) 0.1 gram per cubic metre, so dust capture needs to be at least 99.7% efficient. Methods of capture include electrostatic precipitators and bag-filters. See also cement kiln emissions . Fuels that have been used for primary firing include coal , petroleum coke , heavy fuel oil , natural gas , landfill off-gas and oil refinery flare gas. Because

1469-413: A month for Rosendale cement made it unpopular for constructing highways and bridges, and many states and construction firms turned to Portland cement. Because of the switch to Portland cement, by the end of the 1920s only one of the 15 Rosendale cement companies had survived. But in the early 1930s, builders discovered that, while Portland cement set faster, it was not as durable, especially for highways—to

1582-695: A pozzolan produces a hydraulic mixture (see also: Pozzolanic reaction ), but such concrete was used by the Greeks, specifically the Ancient Macedonians , and three centuries later on a large scale by Roman engineers . There is... a kind of powder which from natural causes produces astonishing results. It is found in the neighborhood of Baiae and in the country belonging to the towns round about Mount Vesuvius . This substance when mixed with lime and rubble not only lends strength to buildings of other kinds but even when piers of it are constructed in

1695-493: 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. 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

1808-741: A very advanced civilisation in El Tajin near Mexico City, in Mexico. A detailed study of the composition of the aggregate and binder show that the aggregate was pumice and the binder was a pozzolanic cement made with volcanic ash and lime. Any preservation of this knowledge in literature from the Middle Ages is unknown, but medieval masons and some military engineers actively used hydraulic cement in structures such as canals , fortresses, harbors , and shipbuilding facilities . A mixture of lime mortar and aggregate with brick or stone facing material

1921-422: Is hydraulic cement , which hardens by hydration of the clinker minerals when water is added. Hydraulic cements (such as Portland cement) are made of a mixture of silicates and oxides, the four main mineral phases of the clinker, abbreviated in the cement chemist notation , being: The silicates are responsible for the cement's mechanical properties — the tricalcium aluminate and brownmillerite are essential for

2034-512: Is pozzolanic , so that ultimate strength is maintained. Because fly ash addition allows a lower concrete water content, early strength can also be maintained. Where good quality cheap fly ash is available, this can be an economic alternative to ordinary Portland cement. Portland pozzolan cement includes fly ash cement, since fly ash is a pozzolan , but also includes cements made from other natural or artificial pozzolans. In countries where volcanic ashes are available (e.g., Italy, Chile, Mexico,

2147-403: Is a binder , a chemical substance used for construction that sets , hardens, and adheres to other materials to bind them together. Cement is seldom used on its own, but rather to bind sand and gravel ( aggregate ) together. Cement mixed with fine aggregate produces mortar for masonry, or with sand and gravel , produces concrete . Concrete is the most widely used material in existence and

2260-520: Is a major emitter of global carbon dioxide emissions . The lime reacts with silicon dioxide to produce dicalcium silicate and tricalcium silicate. The lime also reacts with aluminium oxide to form tricalcium aluminate. In the last step, calcium oxide, aluminium oxide, and ferric oxide react together to form brownmillerite. A less common form of cement is non-hydraulic cement , such as slaked lime ( calcium oxide mixed with water), which hardens by carbonation in contact with carbon dioxide , which

2373-573: Is about 4.4 billion tonnes per year (2021, estimation), of which about half is made in China, followed by India and Vietnam. The cement production process is responsible for nearly 8% (2018) of global CO 2 emissions, which includes heating raw materials in a cement kiln by fuel combustion and release of CO 2 stored in the calcium carbonate (calcination process). Its hydrated products, such as concrete, gradually reabsorb atmospheric CO 2 (carbonation process), compensating for approximately 30% of

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2486-424: Is behind only water as the planet's most-consumed resource. Cements used in construction are usually inorganic , often lime - or calcium silicate -based, and are either hydraulic or less commonly non-hydraulic , depending on the ability of the cement to set in the presence of water (see hydraulic and non-hydraulic lime plaster ). Hydraulic cements (e.g., Portland cement ) set and become adhesive through

2599-417: Is completely evaporated (this process is technically called setting ), the carbonation starts: This reaction is slow, because the partial pressure of carbon dioxide in the air is low (~ 0.4 millibar). The carbonation reaction requires that the dry cement be exposed to air, so the slaked lime is a non-hydraulic cement and cannot be used under water. This process is called the lime cycle . Perhaps

2712-566: Is constantly fed into a rotary kiln, it allowed a continuous manufacturing process to replace lower capacity batch production processes. Calcium aluminate cements were patented in 1908 in France by Jules Bied for better resistance to sulfates. Also in 1908, Thomas Edison experimented with pre-cast concrete in houses in Union, N.J. In the US, after World War One, the long curing time of at least

2825-411: 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 reducing conditions 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

2938-435: Is continually analyzed for O 2 , CO , NO and SO 2 . 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

3051-449: Is extruded into pellets, which are fed to the grate. In this case, the water content of the pellets is 17-20%. Grate preheaters were most popular in the 1950s and 60s, when a typical system would have a grate 28 m long and 4 m wide, and a rotary kiln of 3.9 x 60 m, making 1050 tonnes per day, using about 0.11-0.13 tonnes of coal fuel for every tonne of clinker produced. Systems up to 3000 tonnes per day were installed. The key component of

3164-438: Is immediately blown into the kiln. The advantage of this system is that it is not necessary to store the hazardous ground fuel: it is used as soon as it is made. For this reason it was the system of choice for older kilns. A disadvantage is that the fuel mill has to run all the time: if it breaks down, the kiln has to stop if no backup system is available. In indirect firing, the fuel is ground by an intermittently run mill, and

3277-674: Is more usually added to Portland cement at the concrete mixer. Masonry cements are used for preparing bricklaying mortars and stuccos , and must not be used in concrete. They are usually complex proprietary formulations containing Portland clinker and a number of other ingredients that may include limestone, hydrated lime, air entrainers, retarders, waterproofers, and coloring agents. They are formulated to yield workable mortars that allow rapid and consistent masonry work. Subtle variations of masonry cement in North America are plastic cements and stucco cements. These are designed to produce

3390-460: 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. The objective of kiln operation is to make clinker with the required chemical and physical properties, at the maximum rate that

3503-403: Is present in the air (~ 412 vol. ppm ≃ 0.04 vol. %). First calcium oxide (lime) is produced from calcium carbonate ( limestone or chalk ) by calcination at temperatures above 825 °C (1,517 °F) for about 10 hours at atmospheric pressure : The calcium oxide is then spent (slaked) by mixing it with water to make slaked lime ( calcium hydroxide ): Once the excess water

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3616-402: Is primarily used for dust ( particulates ), NO x ( nitrogen oxides ) and SO 2 ( sulfur dioxide ), while the remaining parameters relevant pursuant to ambient pollution legislation are usually determined discontinuously by individual measurements. The following descriptions of emissions refer to modern kiln plants based on dry process technology. During the clinker burning process CO 2

3729-483: Is responsible for early strength in modern cements. The first cement to consistently contain alite was made by William Aspdin in the early 1840s: This was what we call today "modern" Portland cement. Because of the air of mystery with which William Aspdin surrounded his product, others ( e.g., Vicat and Johnson) have claimed precedence in this invention, but recent analysis of both his concrete and raw cement have shown that William Aspdin's product made at Northfleet , Kent

3842-696: Is site of one of three cement works in Mozambique . Nacala is the terminal of the Nacala railway that connects to the Central East African Railway (CEAR) of Malawi . The railway system was managed by the Railroad Development Corporation until September 2008 when it was sold to a group of Mozambican investors. It is the location of the deep water port of Port of Nacala . A coal terminal, operated by

3955-504: 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

4068-438: Is to make concrete. Portland cement may be grey or white . Portland cement blends are often available as inter-ground mixtures from cement producers, but similar formulations are often also mixed from the ground components at the concrete mixing plant. Portland blast-furnace slag cement , or blast furnace cement (ASTM C595 and EN 197-1 nomenclature respectively), contains up to 95% ground granulated blast furnace slag , with

4181-478: The Isle of Portland , Dorset, England. However, Aspdins' cement was nothing like modern Portland cement but was a first step in its development, called a proto-Portland cement . Joseph Aspdins' son William Aspdin had left his father's company and in his cement manufacturing apparently accidentally produced calcium silicates in the 1840s, a middle step in the development of Portland cement. William Aspdin's innovation

4294-506: The pyroprocessing stage of manufacture of portland and other types of hydraulic cement , in which calcium carbonate reacts with silica -bearing minerals to form a mixture of calcium silicates . Over a billion tonnes of cement are made per year, and cement kilns are the heart of this production process: their capacity usually defines the capacity of the cement plant. As the main energy-consuming and greenhouse-gas–emitting stage of cement manufacture, improvement of kiln efficiency has been

4407-464: 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

4520-497: The use of waste fuels . 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

4633-446: The 1920s, satellite coolers became common and remained in use until recently. These consist of a set (typically 7–9) of tubes attached to the kiln tube. They have the advantage that they are sealed to the kiln, and require no separate drive. From about 1930, the grate cooler was developed. This consists of a perforated grate through which cold air is blown, enclosed in a rectangular chamber. A bed of clinker up to 0.5 m deep moves along

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4746-523: The Art to Prepare a Good Mortar published in St. Petersburg . A few years later in 1825, he published another book, which described various methods of making cement and concrete, and the benefits of cement in the construction of buildings and embankments. Portland cement , the most common type of cement in general use around the world as a basic ingredient of concrete, mortar , stucco , and non-speciality grout ,

4859-543: The New York Commissioner of Highways to construct an experimental section of highway near New Paltz, New York , using one sack of Rosendale to six sacks of Portland cement. It was a success, and for decades the Rosendale-Portland cement blend was used in concrete highway and concrete bridge construction. Cementitious materials have been used as a nuclear waste immobilizing matrix for more than

4972-463: The Philippines), these cements are often the most common form in use. The maximum replacement ratios are generally defined as for Portland-fly ash cement. Portland silica fume cement. Addition of silica fume can yield exceptionally high strengths, and cements containing 5–20% silica fume are occasionally produced, with 10% being the maximum allowed addition under EN 197–1. However, silica fume

5085-678: The Port of Nacala, is located in the town of Nacala-a-Velha on the opposite side of the bay from Nacala. Nacala Airport is a former airbase that has been converted into an international airport. The town is also known for its beaches and scuba diving. There is another town in Mozambique that contains the name Nacala, it is called Nacala-a-Velha ("The Old Nacala"), just across the bay (c. 30km by road). 14°32′34″S 40°40′22″E  /  14.54278°S 40.67278°E  / -14.54278; 40.67278 Cement A cement

5198-616: The absence of pozzolanic ash, the Romans used powdered brick or pottery as a substitute and they may have used crushed tiles for this purpose before discovering natural sources near Rome. The huge dome of the Pantheon in Rome and the massive Baths of Caracalla are examples of ancient structures made from these concretes, many of which still stand. The vast system of Roman aqueducts also made extensive use of hydraulic cement. Roman concrete

5311-630: The air. It is resistant to attack by chemicals after setting. The word "cement" can be traced back to the Ancient Roman term opus caementicium , used to describe masonry resembling modern concrete that was made from crushed rock with burnt lime as binder. The volcanic ash and pulverized brick supplements that were added to the burnt lime, to obtain a hydraulic binder , were later referred to as cementum , cimentum , cäment , and cement . In modern times, organic polymers are sometimes used as cements in concrete. World production of cement

5424-448: 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 silicagel is formed inside the reactive aggregates which develop characteristics internal fissures. This expansive chemical reaction occurring in

5537-530: The available hydraulic limes, visiting their production sites, and noted that the "hydraulicity" of the lime was directly related to the clay content of the limestone used to make it. Smeaton was a civil engineer by profession, and took the idea no further. In the South Atlantic seaboard of the United States, tabby relying on the oyster-shell middens of earlier Native American populations

5650-403: The average output per kiln in, for example, Thailand is twice that in North America. Essential equipment in addition to the kiln tube and the preheater are: Early systems used rotary coolers, which were rotating cylinders similar to the kiln, into which the hot clinker dropped. The combustion air was drawn up through the cooler as the clinker moved down, cascading through the air stream. In

5763-463: 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

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5876-417: The calciner, the extra amount of air drawn through the kiln would cool the kiln flame excessively. The feed is 40-60% calcined before it enters the rotary kiln. 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,

5989-425: 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

6102-454: The central concern of cement manufacturing technology. Emissions from cement kilns are a major source of greenhouse gas emissions , accounting for around 2.5% of non-natural carbon emissions worldwide. A typical process of manufacture consists of three stages: In the second stage, the rawmix is fed into the kiln and gradually heated by contact with the hot gases from combustion of the kiln fuel . Successive chemical reactions take place as

6215-407: 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 . Fuel systems are divided into two categories: In direct firing, the fuel is fed at a controlled rate to the fuel mill, and the fine product

6328-674: The clinker is brought to its peak temperature mainly by radiant heat transfer, and a bright (i.e. high emissivity ) and hot flame is essential for this, high carbon fuels such as coal which produces a luminous flame are often preferred for kiln firing. Where it is cheap and readily available, natural gas is also sometimes used. However, because it produces a much less luminous flame, it tends to result in lower kiln output. In addition to these primary fuels, various combustible waste materials have been fed to kilns. These alternative fuels (AF) include: Cement kilns are an attractive way of disposing of hazardous materials, because of: A notable example

6441-406: The clinker to around 100 °C, at which temperature it can be conveniently conveyed to storage. The cement kiln system is designed to accomplish these processes. Portland cement clinker was first made (in 1825) in a modified form of the traditional static lime kiln . The basic, egg-cup shaped lime kiln was provided with a conical or beehive shaped extension to increase draught and thus obtain

6554-560: The combined feed and flame temperature. SO 2 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

6667-456: The concrete matrix generate high tensile stress in concrete and creates cracks that can ruine a concrete structure. However, hot gas is run to waste so the process is inefficient and increases kiln fuel consumption. In the 1970s the precalciner was pioneered in Japan , and has subsequently become the equipment of choice for new large installations worldwide. The precalciner is a development of

6780-420: The development of new cements. Most famous was Parker's " Roman cement ". This was developed by James Parker in the 1780s, and finally patented in 1796. It was, in fact, nothing like material used by the Romans, but was a "natural cement" made by burning septaria – nodules that are found in certain clay deposits, and that contain both clay minerals and calcium carbonate . The burnt nodules were ground to

6893-415: The development of the rotary kiln , which today accounts for more than 95% of world production. The rotary kiln consists of a tube made from steel plate, and lined with firebrick . The tube slopes slightly (1–4°) and slowly rotates on its axis at between 30 and 250 revolutions per hour. Rawmix is fed in at the upper end, and the rotation of the kiln causes it gradually to move downhill to the other end of

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7006-486: The dust-laden gases leaving simple dry process kilns. If, instead, the entire feed of rawmix is forced to pass through the cyclone, a very efficient heat exchange takes place: the gas is efficiently cooled, hence producing less waste of heat to the atmosphere, and the raw mix is efficiently heated. The heat transfer efficiency is further increased if a number of cyclones are connected in series. The number of cyclones stages used in practice varies from 1 to 6. Energy, in

7119-607: The earliest known occurrence of cement is from twelve million years ago. A deposit of cement was formed after an occurrence of oil shale located adjacent to a bed of limestone burned by natural causes. These ancient deposits were investigated in the 1960s and 1970s. Cement, chemically speaking, is a product that includes lime as the primary binding ingredient, but is far from the first material used for cementation. The Babylonians and Assyrians used bitumen (asphalt or pitch ) to bind together burnt brick or alabaster slabs. In Ancient Egypt , stone blocks were cemented together with

7232-622: 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. Emissions from cement works are determined both by continuous and discontinuous measuring methods, which are described in corresponding national guidelines and standards. Continuous measurement

7345-451: 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

7458-498: 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

7571-439: 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,

7684-541: 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 volatiles are normally milled in an inert atmosphere (e.g. CO 2 ). A large volume of gases has to be moved through

7797-461: The first decade of the nineteenth century. Vicat went on to devise a method of combining chalk and clay into an intimate mixture, and, burning this, produced an "artificial cement" in 1817 considered the "principal forerunner" of Portland cement and "...Edgar Dobbs of Southwark patented a cement of this kind in 1811." In Russia, Egor Cheliev created a new binder by mixing lime and clay. His results were published in 1822 in his book A Treatise on

7910-407: 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,

8023-402: The formation of the liquid phase during the sintering ( firing ) process of clinker at high temperature in the kiln . The chemistry of these reactions is not completely clear and is still the object of research. First, the limestone (calcium carbonate) is burned to remove its carbon, producing lime (calcium oxide) in what is known as a calcination reaction. This single chemical reaction

8136-502: The fuel. In the cooler the air is heated by the cooling clinker, so that it may be 400 to 800 °C before it enters the kiln, thus causing intense and rapid combustion of the fuel. 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,

8249-425: The gas-suspension preheater is the cyclone . A cyclone is a conical vessel into which a dust-bearing gas-stream is passed tangentially. This produces a vortex within the vessel. The gas leaves the vessel through a co-axial "vortex-finder". The solids are thrown to the outside edge of the vessel by centrifugal action, and leave through a valve in the vertex of the cone. Cyclones were originally used to clean up

8362-428: The grate. These coolers have two main advantages: (1) they cool the clinker rapidly, which is desirable from a clinker quality point of view; it avoids that alite ( C 3 S ), thermodynamically unstable below 1250 °C, revert to belite ( C 2 S ) and free CaO (C) on slow cooling: (as alite is responsible for the early strength development in cement setting and hardening, the highest possible content of

8475-448: The higher temperature needed to make cement clinker. For nearly half a century, this design, and minor modifications, remained the only method of manufacture. The kiln was restricted in size by the strength of the chunks of rawmix: if the charge in the kiln collapsed under its own weight, the kiln would be extinguished. For this reason, beehive kilns never made more than 30 tonnes of clinker per batch. A batch took one week to turn around:

8588-426: The initial CO 2 emissions. Cement materials can be classified into two distinct categories: hydraulic cements and non-hydraulic cements according to their respective setting and hardening mechanisms. Hydraulic cement setting and hardening involves hydration reactions and therefore requires water, while non-hydraulic cements only react with a gas and can directly set under air. By far the most common type of cement

8701-418: 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

8814-463: 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

8927-400: The kiln system. Particularly in suspension preheater systems, a high degree of suction has to be developed at the exit of the system to drive this. Fans are also used to force air through the cooler bed, and to propel the fuel into the kiln. Fans account for most of the electric power consumed in the system, typically amounting to 10–15 kW·h per tonne of clinker. The exhaust gases from

9040-406: The kiln, under the flame, is the reaction of belite ( C 2 S = 2CaO·SiO 2 , or Ca 2 SiO 4 ) with calcium oxide to form alite ( C 3 S = 3CaO·SiO 2 , or Ca 3 SiO 5 ): 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

9153-402: The kiln. At the other end fuel, in the form of gas, oil , or pulverized solid fuel, is blown in through the "burner pipe", producing a large concentric flame in the lower part of the kiln tube. As material moves under the flame, it reaches its peak temperature, before dropping out of the kiln tube into the cooler. Air is drawn first through the cooler and then through the kiln for combustion of

9266-405: The limit of size of rotary kilns, because the flexibility of the steel shell becomes unmanageable at or above this size, and the firebrick 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

9379-404: The low pH (8.5–9.5) of its pore water) limited its use as reinforced concrete for building construction. The next development in the manufacture of Portland cement was the introduction of the rotary kiln . It produced a clinker mixture that was both stronger, because more alite (C 3 S) is formed at the higher temperature it achieved (1450 °C), and more homogeneous. Because raw material

9492-439: 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. From the earliest times, two different methods of rawmix preparation were used:

9605-460: The manufacturer, although it produces correspondingly greater emission of CO 2 . Manufacturers who think such emissions should be reduced are abandoning the use of wet process. In the 1930s, significantly, in Germany, the first attempts were made to redesign the kiln system to minimize waste of fuel. This led to two significant developments: The grate preheater consists of a chamber containing

9718-409: The mineral components were either dry-ground to form a flour-like powder, or were wet-ground with added water to produce a fine slurry with the consistency of paint, and with a typical water content of 40–45%. 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

9831-493: 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

9944-465: The other materials in the mix to form calcium silicates and other cementitious compounds. The resulting hard substance, called 'clinker', is then ground with a small amount of gypsum ( CaSO 4 ·2H 2 O ) into a powder to make ordinary Portland cement , the most commonly used type of cement (often referred to as OPC). Portland cement is a basic ingredient of concrete , mortar , and most non-specialty grout . The most common use for Portland cement

10057-474: The point that some states stopped building highways and roads with cement. Bertrain H. Wait, an engineer whose company had helped construct the New York City's Catskill Aqueduct , was impressed with the durability of Rosendale cement, and came up with a blend of both Rosendale and Portland cements that had the good attributes of both. It was highly durable and had a much faster setting time. Wait convinced

10170-442: The preheater. The logical development was to install a specially designed combustion chamber at the base of the preheater, into which pulverized coal is injected. This is referred to as an "air-through" precalciner, because the combustion air for both the kiln fuel and the calciner fuel all passes through the kiln. This kind of precalciner can burn up to 30% (typically 20%) of its fuel in the calciner. If more fuel were injected in

10283-399: 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

10396-418: The rawmix very efficiently. The pellets then drop into the kiln. Very little powdery material is blown out of the kiln. Because the rawmix is damped in order to make pellets, this is referred to as a "semi-dry" process. The grate preheater is also applicable to the "semi-wet" process, in which the rawmix is made as a slurry, which is first de-watered with a high-pressure filter, and the resulting "filter-cake"

10509-399: 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

10622-447: The rest Portland clinker and a little gypsum. All compositions produce high ultimate strength, but as slag content is increased, early strength is reduced, while sulfate resistance increases and heat evolution diminishes. Used as an economic alternative to Portland sulfate-resisting and low-heat cements. Portland-fly ash cement contains up to 40% fly ash under ASTM standards (ASTM C595), or 35% under EN standards (EN 197–1). The fly ash

10735-407: The sea, they set hard underwater. The Greeks used volcanic tuff from the island of Thera as their pozzolan and the Romans used crushed volcanic ash (activated aluminium silicates ) with lime. This mixture could set under water, increasing its resistance to corrosion like rust. The material was called pozzolana from the town of Pozzuoli , west of Naples where volcanic ash was extracted. In

10848-418: The size of kiln will allow, while meeting environmental standards, at the lowest possible operating cost. The kiln is very sensitive to control strategies, and a poorly run kiln can easily double cement plant operating costs. 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

10961-400: The suspension preheater. The philosophy is this: the amount of fuel that can be burned in the kiln is directly related to the size of the kiln. If part of the fuel necessary to burn the rawmix is burned outside the kiln, the output of the system can be increased for a given kiln size. Users of suspension preheaters found that output could be increased by injecting extra fuel into the base of

11074-399: 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

11187-412: The temperature of the rawmix rises: Alite is the characteristic constituent of Portland cement . Typically, a peak temperature of 1400–1450 °C is required to complete the reaction. The partial melting causes the material to aggregate into lumps or nodules, typically of diameter 1–10 mm. This is called clinker. The hot clinker next falls into a cooler which recovers most of its heat, and cools

11300-407: 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: In the case of precalciner kilns, further controls are available: The independent use of fan speed and fuel rate

11413-435: 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

11526-444: Was a true alite-based cement. However, Aspdin's methods were "rule-of-thumb": Vicat is responsible for establishing the chemical basis of these cements, and Johnson established the importance of sintering the mix in the kiln . In the US the first large-scale use of cement was Rosendale cement , a natural cement mined from a massive deposit of dolomite discovered in the early 19th century near Rosendale, New York . Rosendale cement

11639-459: 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

11752-479: Was counterintuitive for manufacturers of "artificial cements", because they required more lime in the mix (a problem for his father), a much higher kiln temperature (and therefore more fuel), and the resulting clinker was very hard and rapidly wore down the millstones , which were the only available grinding technology of the time. Manufacturing costs were therefore considerably higher, but the product set reasonably slowly and developed strength quickly, thus opening up

11865-473: Was developed in England in the mid 19th century, and usually originates from limestone . James Frost produced what he called "British cement" in a similar manner around the same time, but did not obtain a patent until 1822. In 1824, Joseph Aspdin patented a similar material, which he called Portland cement , because the render made from it was in color similar to the prestigious Portland stone quarried on

11978-505: Was extremely popular for the foundation of buildings ( e.g. , Statue of Liberty , Capitol Building , Brooklyn Bridge ) and lining water pipes. Sorel cement , or magnesia-based cement, was patented in 1867 by the Frenchman Stanislas Sorel . It was stronger than Portland cement but its poor water resistance (leaching) and corrosive properties ( pitting corrosion due to the presence of leachable chloride anions and

12091-629: Was formalized by French and British engineers in the 18th century. John Smeaton made an important contribution to the development of cements while planning the construction of the third Eddystone Lighthouse (1755–59) in the English Channel now known as Smeaton's Tower . He needed a hydraulic mortar that would set and develop some strength in the twelve-hour period between successive high tides . He performed experiments with combinations of different limestones and additives including trass and pozzolanas and did exhaustive market research on

12204-417: 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

12317-532: 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,

12430-405: Was rarely used on the outside of buildings. The normal technique was to use brick facing material as the formwork for an infill of mortar mixed with an aggregate of broken pieces of stone, brick, potsherds , recycled chunks of concrete, or other building rubble. Lightweight concrete was designed and used for the construction of structural elements by the pre-Columbian builders who lived in

12543-416: 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

12656-407: Was used in house construction from the 1730s to the 1860s. In Britain particularly, good quality building stone became ever more expensive during a period of rapid growth, and it became a common practice to construct prestige buildings from the new industrial bricks, and to finish them with a stucco to imitate stone. Hydraulic limes were favored for this, but the need for a fast set time encouraged

12769-748: Was used in the Eastern Roman Empire as well as in the West into the Gothic period . The German Rhineland continued to use hydraulic mortar throughout the Middle Ages, having local pozzolana deposits called trass . Tabby is a building material made from oyster shell lime, sand, and whole oyster shells to form a concrete. The Spanish introduced it to the Americas in the sixteenth century. The technical knowledge for making hydraulic cement

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