4 TH Class Supplement BC It

4th Class Power Engineering
(Supplementary Information)
Pulp and Paper Mill Operations Crude Oil Refining
Supplementary Information
Crude Oil Refining
Introduction
Although not required specifically by the 4th class Syllabus, this section has been included in this workbook to provide additional information on crude oil refining. This is intended for those Power Engineers who are working in the oil and gas industry or are interested in these processes and desire more information than is provided in the Learning Modules.
Distillation
As noted earlier in your modules, the many substances in crude oil boil and condense at a different temperature. The process of boiling and then condensing is called distillation. Gasoline, for example, starts to boil into vapor at 32oC but furnace fuel oil will not start to boil until it reaches 200oC and its vapors will condense at temperatures below 200oC. Crude oil refiners make use of these characteristics of the substances in crude oil to separate them from each other. The refineries begin by heating the crude oil inside a furnace to about 345oC. At this temperature, about 65 percent of the crude oil changes to vapor. The vapors go to what is called an atmospheric distillation tower. As the vapors swirl up inside the tower they begin to cool. Those that condense at higher temperatures condense first and collect in trays lower down. Those that condense at the lowest temperatures become liquid in trays near the top.
Supplementary Information Crude Oil Refining Unit B1-10 Workbook 2
HVAC 6012 Psychrometric Properties of Air Unit B1-9 Instructor Guide
The figure shows a distillation tower. Crude oil is heated in a furnace to about 345oC causing most of it to vaporize. The hot crude is discharged into the bottom of the distillation tower where the gases begin to pass upward through the tower and cool. As the gases pass up through the tower they are routed through holes in trays positioned inside the tower. Each of the holes is fitted with a bubble cap. These trays are covered with a layer of liquid hydrocarbon. The bubble caps force the vapors to bubble through this layer of liquid. As the vapors cool, the fractions begin to condense at the appropriate temperature. The condensate builds up on the trays and maintains the level of liquid. Excess liquid overflows into collections headers and is drawn off to the appropriate tanks. The heavier oils condense first and are drawn off. Then the lighter oils and gasolines are drawn off toward the top. Gases which are not condensed are used in other processes.
The unvaporized heavy residue at the bottom is pumped to the vacuum distillation unit. The vacuum permits the residue to boil at lower temperatures so that it may be separated into stocks for light, intermediate, and heavy lubricating oil, vacuum gas oil, and pitch. The vacuum gas oil is further processed into fuels and the pitch is used to make asphalt.
SOPEEC Topic BN; BO Boiler Maintenance; Types of Plants Unit B1-10 - Workbook
Conversion
There are a variety of ways of converting oil. In cracking, one of the main conversion processes, an oil fraction such as gas oil is heated under pressure. This causes its molecules to break down and form smaller molecules of gasoline and light fuel oils. The process not only makes more gasoline from crude oil, it also produces a gasoline with a higher octane than that obtained from distillation. High-octane gasoline is necessary for highcompression engines. Cracking operations are carried out with the aid of a catalyst, a substance that helps a chemical process take place without being affected itself. Another conversion process is alkylation. In the alkylation process, some of these gases pass over a catalyst and their molecules join to make molecules of gasoline. The gasoline so formed is of higher quality than that secured from the distillation process. reforming gets its name from the fact that the process changes the form or shape of gasoline molecules. This is necessary because gasoline from the distillation process is not powerful enough for modern cars; they need higher octanes. One way to do this is to change the molecular structure of the gasoline from the distillation process by reacting to it in the presence of a catalyst containing platinum.
Treating
Nearly all the products that come from distillation, cracking, and other major manufacturing processes contain small amounts of impurities. Some of these give the product a bad odor and others may cause rust or unnecessary wear. Treating removes these impurities. The method of treating used will depend on the product and the impurities that are in it. Some treating methods are simple, such as passing the product through a solution of lye and water, while others are complicated.
Blending
Blending combines various compounds to achieve a product with all the qualities it needs to do its job properly. Gasoline is a good example of a product that must be carefully blended. The gasolines made for use in cars have different qualities than those made for tractors or aircraft. Gasolines are also blended to have different qualities in different seasons. In winter, for example, gasoline is blended to evaporate more readily. One way to do this is by adding butane. This helps the car engine to start quickly in cold weather. Such quick starting would not be possible with the gasoline that is sold in summer.
When gasoline is blended, other substances are added to improve its performance. A special oil is sometimes added to help protect the engine from wear. Other compounds keep the engine clean and prevent the formation of deposits. A substance may be added so that the gasoline will keep well in storage.
Fuels
The oil refiners chief job is making gasoline. Other fuels, however, are important products of most refineries. Kerosene and stove oil are burned in space heaters, cook stoves, and other small, oil-fired appliances. Domestic heating oil is used in oil furnaces in houses. Light industrial fuels are burned in the furnaces of office buildings, apartment houses, and factories. Bunker fuels, which are dark, heavy mixtures, are usually burned in specialized boilers in ships, power-generating stations, and large industrial plants. Diesel fuels cover a wide range of uses. The relatively small diesel engines used in buses operating in the city may run on a product similar to stove oil. Transport trucks, inter-city buses, and cars with diesel engines usually burn a product much like domestic heating oil. Big diesel engines on trains, in power stations, and on ships use a variety of industrial diesel fuels. Aviation fuels are of two types: specially blended gasoline and jet fuel. Jet fuels, used in jet and turbo-prop engines, are made the same way as kerosene; by distillation, treating, and blending. Gases are another important class of fuels. They are produced in most refinery processes and are used in various ways. Some fuel refinery furnaces. Others are liquefied under pressure, put in steel bottles, and sold as LPG (liquefied petroleum gas) to householders as fuel for gas appliances and space heaters.
Lubricating oils, greases, waxes, asphalt

None of the cars, trucks, or machines on farms or in factories would run very long without oil and grease. However, compared with gasoline and fuel oils, lubricating oils and greases are used in small quantities and only a few of the refineries in Canada make them in addition to gasolines and fuel oils.
Refineries throughout the world have different ways of separating and treating lubricating oils to get the products required. These methods include treating with chemicals to separate the various types of oils, to remove wax, and to get rid of impurities. The largest lubricating-oil plant in Canada, which is located in the Imperial Oil refinery at Sarnia, Ont., makes 11 different lubricating oils as bases from which about 550 different products can be blended. Other substances have to be added to the oils to enable them to do special jobs such as preventing rust, sticking to fast-moving machinery, or bearing the weight of heavy equipment.
Greases
It is not always possible to lubricate a machine with a liquid, particularly where the liquid may run off the part it is supposed to lubricate. A common solution to this problem is to use a solid lubricant, usually a grease. Most greases are made by mixing lubricating oil and special soap. The soap holds the oil the way a sponge holds water.
Asphalts
Asphalts for roads, shingles, and other purposes are made from the residues left after the other fractions have been removed. Mixed with sand, gravel, and crushed stone this residue can be used on roads without further processing. Harder asphalt that will not flow is needed for shingles and this is made by blowing air through the hot residue, causing it to harden gradually. The degree of hardness will depend on how much air is blown through.
Inspection and Research

Guarding the quality of the products turned out by a refinery or gas plant is the job of the men and women in the inspection laboratories. Day and night, seven days a week, people are on duty testing samples. They test for color, odor, boiling point, sulphur content, burning and quality. They also perform dozens of other necessary checks. If the inspectors find the quality of a product is not up to standard, they pass this information quickly to the operators who trace the cause and correct it.
Refiners also depend on researchers to find ways of improving the products the refinery is making, to develop new products, and to find easier and cheaper ways of refining oil. All the processes used in the refinery and most of the products that come out of it were developed beforehand in research laboratories.
Supplementary Information Crude Oil Refining Unit B1-10 Workbook
Supplementary Information
Pulp and Paper Mill Operations
Introduction
Although not required by the 4th class Syllabus, this section is included in this workbook to provide additional information on the processes used on pulp and paper mills. This is intended for those Power Engineers who are working in the paper mill industry or are interested in these processes and desire more information than is provided in the Learning Modules.
Pulp and paper Mill Processes

The information provided in the module is limited and a more detailed discussion is provided in this supplement. Most pulp that is used in making paper is manufactured from wood or from old papers (recycle). Wood is made up of cellulose fibers which are bonded together with lignin. Both the cellulose and lignin are organic hydrocarbons having different properties. The cellulose fibers can be compared to a drinking straw consisting of a long tubular cell wall with a hollow center. This cellulose is the base that paper is made from. When paper is produced on a paper machine, the fibers are mixed with water to form a pulp slurry. When this pulp slurry is spread across the wire of the paper machine, the water passes through leaving a mat of fiber that intermingles to form a bond. This is the first stage in the formation of a sheet of paper. Since the sheet consists mostly of cellulose fibers which mesh together, the longer these fibers are, the stronger the sheet. The method of producing the pulp from wood is determined by how long the fibers need to be. Several methods are used to break wood down into cellulose fibers for the production of paper.
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Supplementary Information Pulp and Paper Mill Operations Unit B1-10 Workbook
Although largely produced for the manufacture of paper, wood pulp is also used for many other things. Dissolving grade pulp is used to manufacture cellophane (from cellulose), as well as rayon and other clothing fabrics. Cellulose fibers are also added to foods to act as a binding agent holding foodstuffs together.
Mechanical Pulping
The simplest method of producing pulp is to press short logs against a grinding wheel, to grind the wood up and separate the cellulose fiber mechanically This process is illustrated in Figure 1. Short logs which have had the bark removed are loaded into a magazine where a hydraulic ram presses these logs against a rotating grinding wheel. This causes the wood to be ground up dislodging the fiber. Showers wash and cool the grinding wheel, flushing the fibers off the wheel and down into the basin located below the grinding wheel. The fiber and water slurry is the drawn off this sump and pumped to the paper mill for the manufacture of paper. The pulp produced by this process is very stiff and includes a large amount of lignin. In addition, the cellulose is broken down during the grinding process and very low grade fiber is produced. Figure 1 Mechanical Pulping The paper produced using this process is called mechanical or ground wood paper and is of very low quality. These papers are used for low grade containers such as paper egg cartons. Ground wood pulping is very inexpensive, with the major cost being in the fiber costs (raw logs), and energy cost to run the grinders. In order to improve the quality of the fiber produced by mechanical pulping, the logs are often chipped and then stored in a steaming vessel, where steam is used to heat the chips for several minutes to several hours. The steam penetrates the wood chips, and softens the lignin so that the cellulose fibers more easily detach from each
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other. This reduces the energy costs and allows the chips to be broken down, using a refiner or defibrator instead of the grind stone. Refiners cause less damage to the fiber, and produce longer cellulose fibers that can be used to produce higher quality papers.
Figure 2 Thermo Mechanical Defibrator
The defribrators used in this process consist of circular stationary and rotating plates as shown in the figure. The rotating plate is positioned very close to the stationary plate and both plates are fitted with corrugate surfaces. The softened chips are forced between the rotating and stationary plates by the feed screw. Attrition between the plates and the chips breaks them up into fiber, which is combined with water used for cooling, and discharged from the defibrator as a pulp slurry.
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Interestingly, the friction produced in this pulping process causes the water which is used in the refiner, to boil forming a large quantity of steam. This steam is dirty, but can be used in a heat exchanger, to boiler clean water to produce enough steam to supply the chip steaming vessels. An auxiliary fired boiler is normally used to produce any extra steam required and to start up the system. Although thermo mechanical pulping produces better quality fibers and better paper than mechanical pulping, the quality is still very low because the fibers are mixed with lignin and are badly broken up during the process. This paper is used to produce low quality corrugated board, building papers and used for the production of roofing papers.
Chemical Pulping
In chemical pulping, a digester is used. The digester consists of a pressure vessel into which the wood chips are placed. Cooking liquor is added to the digester along with the chips. The cooking liquor contains chemicals which dissolved the lignin, causing the wood chips to become softer than with heating alone. Once filled with wood and liquor, the digester is heated and pressurized by addition of steam. The pressure in the digester forces the liquor to penetrate into the wood chips more quickly, and the high temperature increases the reaction between the liquor and lignin. There are many types of digesters. Batch digesters are filled with liquor and chips and then closed up and pressurized with steam for the cooking process. Once the cooking is completed, the bottom valves on the digester are opened, and the pressure in the vessel forces the pulp slurry and liquor out into a blow tank. Another process uses continuous digesters like the one shown in figure 3. The digester consists of a series of horizontal tubes which are fitted with internal screw conveyors. The chips are fed into the top tube by a pressurized feeder.
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Figure 3 Continuous Digester Cooking liquor is also added at the top and the mixture is heated by direct injection of steam. The screw conveyor moves the chip plug along the tube until it reaches the opposite end where it drops into the second tube. The screw in this tube moves the chips along to the other end, and drops into the next tube, and so on, until finally the chips are dropped from the last tube to be discharged from the unit into a defibrator.
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In another design, chips are fed into a vertical tower at the top and moved downward through the tower as the stock is drawn off the bottom. Heated cooking liquor is added, along with the chips, and steam is injected at various levels to maintain the temperature and pressure in the vessel. This is the most common type of digester used in modern chemical pulping and is called a Kamyr digester. Chemical pulping consists of several different processes in itself. The process varies according to the type of chemical used and the pressure, temperature and retention time in the digester. Some common pulping processes that are dependant on the cooking chemical used are: Kraft process sulfite process bi-sulfite process soda process
This document will concentrate on the Kraft process, which is by far the most common in Canada. The Kraft process is an improvement over the earlier soda process which is still in use in some mills. The soda process uses sodium hydroxide to dissolve the lignin in the wood chips to break them down. Sodium hydroxide is very active in attacking organic material and tends to attack the cellulose as well as the lignin. To reduce the degradation of the cellulose, the cooking times are usually short being from 5 to 20 minutes in the digester. To further protect the cellulose fibers, soda ash is added to the cooking liquor. Soda ash is sodium carbonate. Later research determined that sodium sulphide was better at protecting the cellulose fibers from attack by the sodium carbonate. Addition of sodium sulphide allows cooking times of up to 8 hours, to ensure that the lignin is well dissolved and allow the wood chips to fall apart easily.
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Kraft Pulping
In Kraft pulping, the digester is filled with wood chips and cooking liquor which is called white liquor. White Kraft cooking liquor is made up of water, cooking chemicals and a number of dead load chemicals, such as salt and spent liquor solids. For this discussion, only the active chemicals will be considered. As mentioned earlier, these active chemicals in the Kraft pulping process are sodium hydroxide (NaOH) (also called caustic soda) and sodium sulphide (Na2S). In the digester, the cooking chemicals are oxidized and lignin is dissolved from the wood. As a result, the white liquor used in the digester is changed as the digester reaction continues. The cooking takes place under pressure and at high temperature. This causes the liquor to soak into the chips in a process called impregnation. After the cooking time is completed, the mixture of spent cooking liquor and chips is discharged from the digester into a blow tank and no defibrator is required. Since the liquor is at saturation temperature in the digester, when the mixture is discharged and the pressure dropped, some of the water in the liquor flashes into steam. This process causes the fibers to be blasted apart as they pass from the digester to the blow tank. The water which is flashed off the liquor forms a stream contaminated steam. This steam has heating value and is often recovered and used in some heating process. In the pulping process, toxic gases are formed which are vented off with the flash steam, or dissolved in the spent liquor. These are called non-condensable gases. These non-condensable gases produce pollution and must be contained. This is discussed in more detail later in this supplement. The slurry discharged from the digester is pumped to the brown stock washers. This consists of the wood cellulose that is to be used for making pulp or paper and the spent liquor used in the digesters. The liquor contains the dissolved lignin from the wood which gives it a dark brown
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color. At this point, the liquor is called black liquor. The brown stock washers consist of screens, where the liquor is drained from the pulp, and the pulp is washed to remove residual chemicals. The black liquor is then pumped to the recovery plant (usually part of the power plant), where the chemicals are recovered. Since the liquor is only about 10 to 15% solids (lignin and chemical) and 85 to 90% water, it is called weak black liquor.
Paper Making
The chemical recovery process is the major topic in this supplement and will be discussed in detail. But first a brief description of the paper making process is included. Paper (or market pulp) is made by processing the pulp fibers which are washed at the brown stock washers.
Figure 4 Paper Making Process
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The figure shows a typical paper making process for a bleached paper product made from 100% virgin fiber. Virgin fiber is cellulose, that has been supplied by chipping logs and breaking down the chips in digesters (or by mechanical means) as discussed earlier. Much of the paper produced today is a mixture of virgin fiber and recycled fiber. Recycled fiber is obtained from paper that is re-pulped using a large pulper which operates on a principle similar to a blender. This process breaks the paper down into pulp once again and new paper is produced from this pulp. Paper is produced with between 5 and 100% recycled fiber. As shown in the figure, raw logs are chipped and stored in large chip bins before going to the digesters. The trees that are used to produce the logs can affect the paper since the cellulose of trees differs from one species to another. Often various species are blended to produce the desired paper qualities. In the digesters, white liquor is mixed with the chips, and the mixture is cooked under pressure by direct injection of steam. In addition, heat exchangers are often used to heat the liquor that is circulated through the digesters. This is important to the Power Engineers because the steam is supplied to the digesters from the power plant. Steam that is injected into the stock inside the pulpers cannot be recovered as condensate. As a result, a lot of makeup feedwater is required for pulp and paper mill boilers. In addition, the liquor heaters present a severe contamination hazard. Usually, the steam used in the liquor heaters is returned as condensate to the power plant, however, this condensate must be constantly monitored to ensure that it is not contaminated by the liquor chemicals. When it is, the condensate must be dumped immediately. White liquor, used in Kraft process digesters has sodium hydroxide and sodium sulphide as the active chemicals. The sodium hydroxide, also called caustic soda is added (or recovered) at the recausticizing plant (recaust).
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The pulp stock produced in the digesters, is discharged into the blow tank where the pressure is reduced from digester pressure to about atmospheric pressure. The stock is then pumped to the brown stock washers, where the black liquor is separated from the pulp fiber and the fiber is washed. The weak black liquor produced at the washers is pumped to the recovery plant. Washed pulp is then screened in the brown stock screen room. Screening removes fiber clumps and knots that are not completely digested in the digester process. In addition to the screens, the pulp is passed through cleaners where dirt particles and fiber fines (to small to be used for paper) are removed. At this point in the process, the pulp is brown in color. This color is due to the fact that some residual lignin remains on the pulp fibers. Pure cellulose is very white in color. Cotton from cotton plants is actually pure cellulose that has leaked out of the plant. If the paper mill produces brown paper such as that used for the manufacture of boxes and bags, then the pulp is used as is comes from the screen room. If the paper mill produces white paper, however, the stock is passed through a bleaching process where the remaining lignin is removed. Bleaching is really an extension to the digester reaction where more lignin is removed using different chemicals. Many chemicals are used for bleaching including oxygen, chlorine, sulphur dioxide, sodium hypochlorite etc. The bleaching process must be carefully monitored because it can cause the production of toxic materials resulting in pollution. The stock is heated in the bleach plant also. This heating is done by injecting steam into the bleaching towers, and therefore, the condensate is not recovered. In some cases, heat exchangers may be used for heating bleaching chemicals and some condensate may be returned. After bleaching, the stock goes to the bleached screen room, where it is screened again and passed through a large number of centrifugal cleaners, to remove fines that are produced, as a result of the bleaching process.
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The pulp stock is now ready to be used in the production of paper. It is normally screened on thickeners to remove excess water to reduce storage requirements. The dewatered stock is then stored in the high density chest until required by the paper machine. The best way to describe how paper is produced is to say that huge quantities of water are added to the pulp fiber in stages and then the water is removed in stages as the sheet is formed and dried. Water is added as the pulp stock approaches the paper machine, until the consistency is less than 1% stock fiber in 99% water. This low consistence slurry is then pumped through a final set of pressure screens to the paper machine headbox.
Figure 5 Paper Machine The paper machine is the heart of the paper making process. This is a huge machine with several major sections and is operated by highly skilled paper makers. A typical paper machine is 7.5 meters wide and 100 meters long. There are many different types of paper machine but the majority have the same major sections, although each section many have various configurations.
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The first section of the paper machine is the forming section which starts at the headbox. Low consistency stock is pumped to the headbox. The headbox is usually a closed chamber designed to keep the stock in suspension, and stop the fibers from collecting into lumps (flocking). A thin opening along the edge of the headbox allows the stock to flow (squirt) out along the entire width of the machine. This opening is called the slice, and is adjustable to ensure the same amount of stock exits the headbox, along the entire width so that the sheet formed is consistent thickness (caliper). The stock is discharged from the headbox onto a forming wire. The forming wire is traveling along the machine and as the stock squirts from the headbox, and lands on the forming wire, the water passes through the wire. This results in a mat of pulp fiber building up on the wire forming the initial sheet of paper. There are many types of paper machine formers. The one shown in this figure is called a Fourdrinier, which is the most common but is being superseded by new types of formers. Most of the newer formers use more than one wire, and the headbox discharges into the nip between two moving wires. This forms a more consistent paper sheet. Often paper is produced in layers, where several small formers are used to produce thin layers of paper, one on top of the other until the required thickness is achieved. These layers are formed on separate wires traveling around cylinders and are called cylinder machines. Few of these are made today but many still exist. One advantage to a cylinder machine is that different fibers can be supplied to each layer. For example, the bottom layers can be cheaper brown fiber, and the top layer can be bleached stock for better printing characteristics. This results in a paper that is brown on one side and white on the other like many cereal boxes. Fourdrinier machines can also produce paper in layers with one or two wires above the bottom wire, each with a separate headbox.
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Figure 6: Twin Wire Former This figure shows a twin wire former which is used to produce a two ply sheet. A second forming wire is positioned above the bottom wire, and a thin sheet is produced on each forming wire. These two sheets then come together to form a consolidated sheet, which continues along the bottom forming wire until it reaches the suction roll (couch roll) at the end of the forming section. Many other configurations using several forming wires are also produced but are beyond the scope of this course. Note that there are several devices used to assist in removing water from the sheet as it moves along the forming wires. First the water flows naturally through the wire, but soon a fiber mat builds up which restricts the water flow. Then, foil boxes are used with foils, which act against the bottom of the wire forming a very slight vacuum to assist water flow from the sheet. After the foil boxes are flat boxes. The flat boxes are connected to vacuum pumps. The vacuum in the flat boxes further assists in removing water from the sheet. As the sheet proceeds down the wire, the vacuum in each consecutive set of flat boxes is increased. The greatest vacuum is in the roll at the end of the forming section called the couch roll.
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As you can see, a lot of water is drained from the stock on the former. Many paper machines produce 1000 tons of paper a day or more. If the consistency at the headbox is 1%, it means that 100 tons of stock at the headbox produces 1 ton of paper. To produce 1000 tonnes of paper, 100 000 tonnes of stock passes though the headbox and therefore, 99 000 tonnes of water is removed on the paper machine. About 50% of this is removed in the forming section as liquid water. This means that over 4000 cubic meters of water is added to the stock per hour, as it approaches the paper machine. Most of this water is then drained off at the former. If fresh water was used in paper making, a tremendous amount of water would be required, and a huge volume of effluent would be produced. To avoid this, the water drained from the former is recovered and added back into the stock approaching the headbox. This water is also filled with additives and fines, so that recycling the water not only reduces water usage, but also recovers the chemicals and fines. In a bleached paper mill, the fines give the recycled water a milky appearance and the water is called white water. In brown paper mills the recycled water is brown but is still called white water. There is a limit as to how much water can be drained from the sheet in the forming section, and the sheet still has about 55% moisture content when it leaves the former. This moisture content must be reduced to about 5% for the finished paper product. Further, water removal is achieved in the press and dryer sections of the paper machine.
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Figure 7 Paper Machine Press Section
The sheet is picked up off the former and transferred to the press section. Since the paper machine is running at speeds of 500 meters per second, or more, the speed of each section of the machine must be carefully controlled to avoid slack or tearing the sheet. Normally the sheet is transferred to a felt on the press. In the example shown in the figure, the press has two sets of press rolls. The paper sheet is sandwiched between two press felts passing through each press, and carried by the felts through the press nips. Hydraulic pressure acts to force the press rolls together and squeeze water from the sheet. The water is transferred through the press felts and into holes drilled in the press roll covers. As the rolls rotate the water is thrown clear.
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The press felts are equipped with high pressure showers and vacuum boxes, that clean and remove excess water from the felts on a continuous basis. Pressing removes another 5% or so of the water from the sheet, and also helps to consolidate the sheet by pressing the fibers together to form a better bond. This makes the sheet stronger and easier to transfer from one section of the machine to the next. After the press section, the remaining water is removed from the sheet in the dryers.
Figure 8 Paper Machine Dryers
The longest section of the paper machine are the dryers. In most machines, this consists of a series of rotating steel drums which are heated using steam. The sheet leaves the press section and passes around the first dryer cylinder. In this example, the sheet passes around the bottom side of the first dryer cylinder. The sheet then passes around the top of the second cylinder and bottom of the third and so on. The sheet weaves its way through the dryer around all the cylinders, until it reaches the end where the moisture content has been reduced to the desired value.
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Each of the dryer cylinders is heated with steam. As the sheet passes around each cylinder, it is heated by the hot steel of the cylinder. This causes the water to be evaporated from the sheet as is moves along the dryers. On most of the dryer cylinders a felt is used. The felt assists in pressing the sheet against the cylinders and helps transfer heat. As the water evaporates, air surrounding the dryer cylinders becomes very moist. As you know from air conditioning theory, when the humidity reaches 100% no more water will be evaporated. Therefore, the dryer is supplied with warm fresh air and moist air is continuously vented. Most dryers are enclosed at the top, or completely enclosed by a dryer hood where the atmosphere is carefully controlled. Steam from the power plant is admitted to the rotating dryer cylinders and condensate formed in the dryer is drawn off and returned to the power plant. The dryers use a large volume of steam. If the sheet is 50% water when it enters the dryer and 5% water when it leaves, one tonne of paper will have about 950 kg of water evaporated from it in the dryers. If the machine produces 1000 tonnes of paper per day, 950 tonnes of water must be evaporated. This is done by transferring heat from steam which is condensing. Therefore, approximately 950 tonnes of steam is required (this various according to steam pressures in the dryer cylinders). This paper machine would consume about 40 000 kg of steam per hour. The condensate produced by the paper machine dryers is clean, and can normally be returned to the power plant for use as feedwater.
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Figure 9 Calendar and Reel After the dryer, the paper is finished if it is a simple paper such as used for newsprint, boxes, bags etc. or if it is to be sold as pulp to other mills. If the machine is used to produce fine paper such as writing paper, the sheet is coated with various materials which are used to fill in voids to make the paper smoother and to give it a white surface. In any case, after drying is completed, the sheet usually passes through a calendar and scanner and is then rolled up onto a large roll at the reel. This roll is called a jumbo and is a completed product except that it is too large to ship to customers. The calendar is used to give the sheet the desired surface properties and caliper. There are many types of calendars. Some have heated or cooled rolls, and some used controlled crown rolls that can apply more pressure between them, at various points across the machine to control sheet caliper. Some calendars have several rolls and the sheet passes through several nips between these rolls. The type of calendar used depends on the quality and type of paper to be produced, as well as technology available at the time of production.
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The scanner consists of an analyzing head that moves back and forth across the sheet and scans it continuously for such things as caliper, moisture content, color, or whatever the desired characteristic of the finished sheet are. The scanner may provide information only for the operators, or it may control various parts of the machine such as the headbox slice, steam to the dryers or moisturizing steam showers. The purpose of the reel is to continuously wind up the sheet as it comes out of the dryer. The reel includes a method of cutting the sheet, and changing the roll core to a new roll, while the machine is operating at full speed. To do this an empty core is brought up to the speed of the jumbo, and then the sheet is cut and transferred to the new core. In the figure, a new core has just been started, and the full jumbo roll is allowed to roll away from the reel to make room for rotating the new core onto the rails. The finished paper is now ready to be cut into smaller rolls or sheets and sent to the customers. The jumbo roll is hoisted off the machine by a crane and transferred to a winder, if it is to be cut into smaller rolls. If the jumbo is to be cut into sheets, it is transferred to a sheet cutter called a layboy. This discussion has provided a brief description of the paper making process. Remember that there are many variables that have not been discussed, depending on the type of paper to be produced, and the type of fiber available. No two paper mills are the same although many of the components are similar.
Mill Power Plant

The power plant in a paper mill supplies many of the requirements of the mill. These include: steam for process electricity, whether generated on site or purchased compressed air for process and for instrumentation water for the process, fire fighting, and for drinking (as well as boiler feedwater) cooking liquor for the digesters
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In addition to these utilities, the power plant is usually responsible for the effluent treatment plant. The production of steam, electricity and compressed air have been discussed in other parts of this course and will not be discussed here. Also, effluent treatment and water processing is discussed in other areas. The remainder of this supplement deals only with the production and recovery of cooking chemicals in a Kraft paper mill.
Figure 10 Digester
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In the Kraft process wood chips are soaked for several hours in white liquor. During this period, the digester is heated and pressurized with steam at about 1000 kPa. Chemical reactions which take place in the digester, as the lignin is dissolved, cause the chemicals in the white liquor to be oxidized forming different compounds. As discussed earlier, the active chemicals in white liquor are sodium hydroxide (NaOH) also known as caustic and sodium sulphide (Na2SO4). The sodium hydroxide is oxidized to sodium carbonate (Na2CO3) in the digester, and the sodium sulphide is oxidized to sodium sulfate (Na2SO4). If a new chemical was used in the digester all the time, the cost of chemicals would make the Kraft process too expensive. Also, there would be a huge amount of spent chemical to dispose of. Therefore, it is essential to the process that the chemicals used in the digester are recovered and used over and over. In other words, the sodium carbonate and sodium sulfate in the black liquor must be converted back to sodium hydroxide and sodium sulphide respectively. In order to convert these chemicals, they must first be separated from the other constituents in the black liquor which are mostly water and lignin. In addition, dirt and other contaminants that get into the chemicals must be removed. There are two major processes which the black liquor is subjected to in order to convert it back into white liquor for reuse in the digesters. The first of these takes place in the recovery boiler and the second takes place in the recausticizing plant (recaust). The recovery boiler is the responsibility of the Power Engineers in a paper mill and the recaust usually also falls under the power house operations and may or may not be operated by Power Engineers. These processes are critical to the operation of the paper mill and are also hazardous areas in which to work.
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Evaporation
The first step in converting black liquor to white liquor is to remove the water from the black liquor. This is done in various types of evaporator and then in the recovery boiler furnace. The evaporators remove most of the water from the liquor to increase the solids concentration to at least 60%. At this concentration, the remaining lignin in the black liquor can be burned in the recovery furnace. Burning the lignin from the black liquor works to remove the lignin, and provides the heat required to evaporate the remaining water from the liquor, and also causes the chemicals to melt. The molten chemical flows from the bottom of the recovery furnace as a smelt. It is very critical that the solids concentration of the black liquor be 60% or more before the liquor is burned. If the solids are lower than this, the excess water causes the furnace to be cooled too much and the liquor will not burn properly. More importantly, the water in the liquor must be evaporated in suspension because if any water reaches the molten smelt at the bottom of the recovery furnace, a smelt-water reaction can occur. Smelt-water reactions make recovery boiler operation very hazardous. A smelt-water reaction is a steam explosion that can be catastrophic. Many early recovery boilers were destroyed, and operators killed by recovery furnace explosions due to smelt-water reactions. When a small amount of water leaks onto the molten smelt bed, it can be caused to flash into steam very rapidly. This rapid flashing means that suddenly the small volume of water is turned into a very large volume of steam. The sudden increase in volume results in an explosion similar to dynamite. This explosion alone can destroy a recovery boiler but also often results in failure of the boiler, itself resulting in a subsequent boiler explosion. Since the liquor has water in it, and the boiler tubes surrounding the recovery furnace are filled with water, extreme care and maintenance must be exercised with recovery boilers to ensure that water does not reach the smelt in the furnace.
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Figure 11 Evaporation
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The weak black liquor is evaporated before firing to form strong black liquor which is about 50% solids concentration. The strong black liquor then passes through a second evaporation process, to produce heavy black liquor at 60% solids or higher for firing in the recovery boiler. Evaporating the water from the liquor begins in multiple effect evaporators. Multiple effect evaporators are large heat exchangers (usually shell and tube), which use steam to evaporate water from the liquor. After the multiple effect evaporators, the second evaporator stage varies from paper mill to paper mill. Traditionally, hot flue gases from the recovery boiler were used to concentrate the liquor to 60%. In this process, the liquor is sprayed into the flue gases and heat, in the flue gases, is used to evaporate water from the liquor. This has the added benefit of scrubbing the flue gases, removing solids that are carried over form the furnace. However, the hot flue gases also evaporate some volatile matter from the liquor which is carried with the flue gases to the stack. This volatile organic matter contributes to the smell of a Kraft paper mill and results in added pollution. Therefore, these direct contact evaporators are no longer installed although some remain in use. There are two major types of direct contact evaporator: cascade evaporator cyclone evaporator
The cascade evaporator consists of a rotating wheel similar in appearance to the paddlewheel on an old ship. The horizontal slats, however, are actually flattened out tubes. This wheel is suspended in a vat filled with strong black liquor so that the wheel is about 40% submerged. A motor rotates the wheel slowly. The strong black liquor coats the tubes, and is lifted from the vat by the rotation of the wheel. The liquor then cascades back into the vat. Flue gases from the boiler economizer pass through the upper portion of the cascade evaporator. The flue gases pass around and through the tubes of the wheel, coming into direct contact with the cascading strong black liquor.
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A large amount of chemical called saltcake carries over from the furnace with the flue gases. The saltcake is re-dissolved in the strong black liquor. Heat in the flue gases also causes the water in the strong black liquor to be evaporated. The combination of evaporation and re-dissolving chemical increases the concentration of the liquor from about 50% to over 60% thus forming heavy black liquor. The flow of liquor from the cascade evaporator is controlled to maintain the desired concentration. From the cascade evaporator, the liquor is pumped immediately to the burners. Because of its concentration, the liquor will become very viscous and difficult to remove from pumps and piping, if it is not kept hot and in motion. When shutting down, the evaporator, pumps and piping must be flushed out immediately using steam and water. The second common type of direct contact evaporator is the cyclone evaporator. Cyclone evaporators are large vertical vessels with conical bottoms. Strong black liquor is supplied to the cyclone evaporator from the multiple effect evaporators. Pumps located at the bottom of the cyclone draw liquor from the cyclone and pump it to the top. The liquor is sprayed through nozzles at the top of the cyclone onto the walls and flows down the walls to the bottom. Another set of nozzles is located at the flue gas inlet to the cyclone where liquor is sprayed into the entering flue gases. The flue gases from the boiler economizer enter the cyclone evaporator at a tangent and swirl around the inside of the unit. Saltcake particles in the flue gases are thrown out by centrifugal force, and become imbedded in the liquor flowing down the walls. This re-dissolves the saltcake. Heat in the flue gases also evaporates water from the liquor, and the solids concentration is increased to above 60% forming heavy black liquor. The heavy black liquor is pumped immediately to the burners.
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Both cascade evaporators and cyclone evaporators require a lot of monitoring to ensure that they are operating properly. Remember that the liquor in the evaporators is a fuel, and that the hot gases can have embers, which may cause fires in the direct contact evaporators that are very difficult to extinguish. Heavy black liquor also causes plug gauges in lines and connections such as instrument fittings and drains. Steam connections are used throughout the system to heat and blow lines clear as necessary. Modern paper mills and refitted mills use low odour recovery boilers, and concentrate the liquor to 60% in steam heated evaporators called concentrators or crystallizers. These use heat exchangers similar to the multiple effect evaporators, but are designed to handle high liquor solids concentrations that tend to scale up conventional multiple effect evaporators.
Multiple Effect Evaporators

The first stage of evaporation in the multiple effect evaporators involves several stages of evaporation. Typically five or six evaporator stages or effects are used. Steam is used to heat the liquor in the first effect. The steam causes the liquor in the first effect to boil. Steam produced by boiling liquor in the first effect is then used to heat the second effect causing the liquor to boil in this vessel also. The steam produced in the second effect is used to heat the third effect and so on.
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Figure 12 Two Evaporator Effects (Falling Film) This figure shows the first two evaporator effects from a typical a set of six. Each effect consists of a vertical shell and tube heat exchanger with a chamber at he bottom. Black liquor is stored in the lower chamber of each evaporator effect. A circulating pump draws black liquor from the bottom chamber and pumps it to the top of the evaporator effect. The liquor flows out over the top tube
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sheet and down through the tubes of the heat exchanger back to the bottom storage chamber. This is called a falling film evaporator because the liquor flows downward as a film coating the inside of the heat exchanger tubes. The tubes are not filled with liquor. The liquor coats the tubes and an empty space is formed inside the ring of falling liquor. Referring to the figure, the liquor falling downward through the tubes in the first effect is heated by live steam that surrounds the tubes. The steam is supplied from the paper mill low pressure steam system which is normally via turbine exhaust or extraction. In this example, the steam pressure to the first effect is 200 psi. Note that each effect is actually divided into two sections: steam side (or vapour side) liquor side
Steam fills the steam side of the first effect on the outside of the heat exchanger tubes. There is no contact between the liquor and steam. As the steam gives up its heat to the liquor it condenses. The condensate formed is drawn off the bottom of the heat exchanger section of the evaporator effect. The liquor circulating through the tubes is heated by the steam outside the tubes and boils. Since the center of the tubes is empty with this type of evaporator, the steam collects in the center of the tubes and is drawn downward to the bottom chamber. The steam formed inside the evaporator is commonly called vapour to differentiate it from the live steam on the steam side of the first effect. In the evaporator shown here, the vapour is drawn off the top of the storage section in the bottom of the evaporator. This causes the vapours to flow down through the tubes to the bottom. In the bottom section of the evaporator, the vapours are separated from the remaining liquor. The liquor is circulated through the evaporator again and the vapours are drawn off to the next effect.
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Note that the pressure on the liquor side of the first effect is lower than the pressure on the steam side. This is very important. If the steam and liquor in the first effect were at the same pressure, they would be at the same temperature because they are both at saturation temperature (one is condensing and the other is boiling). If the liquor and steam are at the same temperature there will be no heat transfer because heat only travels from a substance at a higher temperature to one at a lower temperature. If there is no heat transfer, the liquor does not evaporate and no steam (vapour) is produced in the vapour side of the first effect. Therefore, there is no heat source for the second effect and the whole evaporator system shuts down. It is very important that a difference in pressure exists between the vapour side and the steam side in every effect, or the evaporators will stop working. The power engineer must carefully monitor these pressures and ensure that this differential is maintained. The same process takes place in the second effect of the multiple effect evaporators. Vapour produced in the first effect is used to heat the liquor in the second effect. The pressure on the vapour side of the second effect is the same as the pressure on the liquor side of the first effect. The pressure on the liquor side of the second effect is lower to ensure heat transfer. This continues from each effect to the next until the last effect of the evaporators. Since the pressure drops in each effect, you can see that in the third and subsequent effects, the pressure will be below atmospheric pressure. The vapour produced in the last effect of the evaporators goes to a surface condenser. The surface condenser is another heat exchanger which uses water in the tubes to condense the vapours from the last effect of the evaporators. This, in turn, heats the water slightly which is normally stored for use in the paper mill processes. Condensing the large volume of vapour from the last effect into water in the condenser creates a vacuum. This vacuum maintains the low pressure in the last few evaporator effects. The lowest pressure in the system is in the condenser which is typically about 680 mm Hg (27Hg).
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The only place that live steam is used for heating in the evaporators is the first effect. The steam is condensed in the first effect to form clean condensate, which can be reused as boiler feedwater as long as it is not contaminated. The vapour produced in each effect and used to heat the following effect is also condensed. This vapour is not clean, however, as it contains volatile gases from the liquor, as well as liquor droplets carried over from the previous effect. The condensate drawn off all except the first effect is called contaminated condensate, or process condensate or combined condensate depending on the mill. Contaminated condensate is also drawn off the condenser, where the vapours from the last evaporator effect are condensed. The contaminated condensate is collected and used for the production of white liquor as discussed later in this supplement. The volatile organic material in the liquor which is driven off in the evaporators do not condense in the following effect. These non-condensable gases would soon fill the evaporator heat exchanger, and cause the pressure to increase stopping operation of the units. Also, any non-condensable gases in the steam to the first effect must be vented. Since the first effect is heated with clean steam and is above atmospheric pressure, the non-condensable gases can be vented to atmosphere. However, the remaining effects have toxic noncondensable gases which cannot be vented to atmosphere. A line from each effect leads to a non-condensable header. The non-condensable header in turn leads to the condenser where the lowest pressure exists. The non-condensable gases are, therefore, drawn off each effect to the condenser. A non-condensable valve is provided in the line from each effect. This valve can be adjusted to control the volume of non-condensable gases drawn off the effect. This valve is used to control the pressure in each effect to some degree. The non-condensable gases are drawn off the condenser by ejectors, and sent to the power boiler or lime kiln to be burned.
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The second common type of multiple effect evaporator called a rising film evaporator is shown in the figure below.
Figure 13 Two Evaporator Effects (Rising Film) In these evaporators, the liquor flows upward through the tubes. In rising film evaporators, there is no storage chamber at the bottom, and the liquor is pumped into the heat exchanger at the bottom and rises through the tubes to overflow into a storage chamber at the top. As a result the tubes are flooded with liquor. In these units, the liquor only passes through the evaporator tubes one time. Although fewer pumps are required, rising film evaporators are more difficult to control, and tend to scale at the point where boiling begins inside the tubes. In a falling film unit, all the liquor is at the saturation temperature and boiling is more uniform. In a rising film unit, the liquor is heated as it rises upward through the tubes. At some point the liquor begins to boil.
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This level in the tubes tend to become scaled. All evaporators require cleaning out at some point. The units are frequently boiled out by passing weak black liquor the entire set, and returning it to the weak black liquor storage tank. This is done with little or no steam on and the weak liquor washes out the strong black liquor. Periodically, most evaporators will require a detailed cleaning where high pressure water is used to hydroblast buildup from the tubes, piping, and heat exchangers.
Typical Multiple Effect Evaporator Set

This figure shows a complete set of multiple effect evaporators. These are falling film evaporators and there are six evaporator effects. All effects are similar to the ones illustrated in the figure showing two falling film units.
Figure 14 Typical Multiple Effect Evaporator Set
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Evaporators are numbered according to the flow of steam. Live steam enters the first effect. The steam is supplied from a 280 kPa header in this example. The steam flow is regulated by a control valve to maintain the pressure in the first effect. The steam used in the evaporators must be at saturation temperature. Superheated steam can cause scaling problems in the evaporators. Vapour from the first effect goes to heat the second effect and so on. The flow of liquor through the evaporators can vary. In this example, the weak black liquor from the brown stock washers enters the fourth effect. Some water is evaporated from the liquor in the fourth effect. Liquor is circulated through each effect by a circulating pump. The fourth effect circulating pump also supplies liquor to the fifth effect to maintain level in the fifth effect. The liquor is then transferred from the fifth to the sixth effect. A separate liquor transfer pump is used to pump liquor from the sixth effect to the third effect, and then the liquor flow from the third to the second and to the first effects. Recall that the first effect is at a positive pressure. The liquor from the first effect flows to a flash tank where the pressure is dropped to about atmospheric. Note that the flash tank vents to the inlet of the third effect, where pressure (in this example) is close to atmospheric. As the liquor is flashed in the product flash tank more water is removed. The final product is drawn off the flash tank and pumped to the strong black liquor storage tank. The steam used in the first effect is condensed. The clean condensate is then pumped back to the power house for re-use in the boilers. The vapour condensed in the second to sixth effect and in the surface condenser is called process condensate at this mill. Second effect condensate is pumped to the third effect but from there to the sixth effect, the process condensate flows by differential pressure. Since the pressure in each effect is lower, no pump is required. The combined condensate from the surface condenser also flows by gravity but this is assisted by head pressure. The surface condenser is much higher than the evaporators so that the condensate flows down to the condensate pot.
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The condensate pot is at a vacuum of the sixth effect, and the condensate is pumped from the condensate pot to the process condensate storage tank. Non-condensable gases are produced when the steam and vapours are condensed, in each effect of the evaporators and in the surface condenser. The NCGs from the first effect are vented to atmosphere. NCGs from the remaining effects are directed to a header that carries them to the surface condenser where the pressure is the lowest. All of the NCGs, therefore, end up in the surface condenser. These NCGs are then drawn off the surface condenser by steam operated ejectors. The NCGs mix with the steam and the mixture is discharged into the ejector condenser. The ejector condenser is used to condense the steam from the ejectors, and also any steam carried over from the surface condenser. There are two ejectors to increase the pressure from the vacuum in the surface condenser to above atmospheric pressure. The first stage ejector draws NCGs from the surface condenser, and discharges into the ejector condenser where the steam is condensed. The NCGs are then drawn from the first stage ejector condenser, and discharged to the second stage ejector condenser (both condensers are in the same shell). The steam from the second stage ejector is condensed and the NCGs are now vented to the lime kiln where they are burned. The strong black liquor produced in the multiple effect evaporators is about 50% solids concentration. Additional water must be removed before this liquor can be burned, but it is difficult to increase the solids concentration further in standard evaporators. At this point, the liquor is so thick that it flows very slowly and any more evaporation on the tubes causes scaling problems.
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Concentrator
To reduce scaling and plugging problems, the strong black liquor is evaporated to heavy black liquor in a direct contact evaporator as discussed earlier or in a concentrator (more modern). The concentrator uses steam to evaporate water also, but the design is different than the multiple effect evaporators. The concentrator shown in the figure consists of an elevated liquor vessel with two circulating pumps and two heat exchangers. Strong black liquor from the multiple effect evaporators is pumped into the suction side of one circulating pump at a time.
Figure 15 Typical Concentrator The entering strong black liquor is circulated through the heat exchanger on the left side in this figure. The steam is shut off to this heat exchanger, and the circulating liquor helps to clean the tubes and piping on this side. Strong black liquor is drawn off the left side of the liquor chamber and flows into the pump suction on the right side. This
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liquor is circulated through the right heat exchange which is in service. Steam entering the heat exchanger heats the liquor, but it does not evaporate any water inside the heat exchanger. This is because the heat exchanger is under pressure due to the pump. The liquor in the line from the heat exchanger up to the liquor vessel and in the liquor vessel, produces backpressure due to the head of liquor. This pressure keeps the liquor below its saturation temperature in the heat exchanger because of this increased pressure. The liquor flows from the heat exchanger to the liquor vessel. The pressure in the liquor vessel is lower causing water in the liquor to flash off. The flash steam is drawn off and used to heat the second effect. This unit is a two effect system although some use only one. The vapour from the last effect is condensed in a surface condenser. After several hours of operation, the tubes in the heat exchanger tend to become scaled. This is reduced by switching over the sides, so that the weaker strong black liquor is admitted to the left side and the product drawn off the right. The steam is then shut off the right side and opened up to the left side. Once the liquor has been evaporated to about 60% solids, it is stored in a conical bottom tank with an agitator to ensure it is kept hot and in motion at all times. As soon as possible the liquor is burned in the recovery boiler.
Heavy Black Liquor System

Heavy black liquor is pumped from the heavy black liquor storage tanks, or from the direct contact evaporator to the recovery boiler furnace, by the heavy black liquor pumps sometimes called nozzle pumps. The liquor is usually supplied to several liquor burning nozzles by a ring header that passes around the recovery boiler on the firing floor.
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Figure 16 Recovery Furnace Liquor nozzles are normally located on two sides of the recovery boiler furnace but may be on all four. The liquor is sprayed through the liquor nozzles into the furnace. The nozzles may be stationary or oscillating units. Although oscillating nozzles were used almost exclusively in the past, stationary nozzles have become more common today. The nozzles are easily removed by undoing clamps and hose couplings to allow them to be removed for cleaning. Cleaning liquor nozzles is a constant maintenance task as they easily become plugged and scaled up with heavy black liquor and carbon at the tips. Two refractometers are provided on the heavy black liquor line just before the ring header. These units constantly measure the liquor solids concentration. If liquor solids is
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below a critical value (typically 56%) the refractometers provide a low liquor solids alarm and divert the liquor back to the heavy black liquor storage. This is necessary to avoid a smelt-water reaction which could result from low liquor concentrations. Two refractometers are used with automatic purging to ensure accurate measurement at all times. The heavy black liquor is sprayed into the furnace where the high furnace temperature evaporates the remaining water. This results in the liquor solids forming porous balls like popcorn, that tend to float around the furnace as the organic matter in the liquor burns. As these liquor particles become heavier, they settle to the bottom of the recovery furnace, forming a bed of char that continues to burn on the floor of the recovery boiler. As the carbon is burned off the char bed, the chemicals in the liquor are reduced and melt. The molten chemical forms a liquid on the floor of the recovery boiler called smelt. The smelt formed is a combination of sodium carbonate from the black liquor and sodium sufide. The sodium sulphide is formed in the recovery boiler furnace from sodium sulfate. Recall that sodium sulphide is one of the chemicals used in the digesters and supplied in the white liquor. This chemical is recovered for re-use in the recovery boiler. Air is supplied to the recovery boiler furnace by forced draft fans. The air enters the furnace in stages. Primary air is supplied at the bottom of the furnace around the char bed. This air is necessary to supply oxygen for combustion, and also to ensure that the char bed is kept away from the walls of the furnace. Primary air ports are located along the furnace walls at the bottom. These ports pass through the wall between the wall tubes. If the char is allowed to contact the wall, the cooler tubes will cause the char to freeze forming a solid mass and blocking the primary air ports. This situation is called a blackout, and must be attended to immediately, as the loss of primary air will reduce recovery boiler performance. Blackouts are cleared by using bars and torches, to break loose and melt the solids from around the primary air ports.
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During operation of the recovery boiler the primary air ports must be monitored and cleaned out continuously by the operators to ensure that they do not become plugged. Plugging of individual primary air ports contributes to blackouts. Modern recovery boilers often have automatic port rodders which clear the ports continuously. The primary air added around the smelt bed does not provide adequate oxygen to burn all the organics in the char and, as a result, a large amount of carbon monoxide is produced in this area: C carbon + O2 insufficient oxygen CO carbon monoxide
The carbon monoxide produced then reacts with sodium sulfate in the char, reducing it to sodium sulphide: Na2SO4 + Sodium sulfate 4 CO Carbon monoxide Na2S Sodium sulphide + 4 CO2 Carbon dioxide
This produces the sodium sulphide required in white liquor and removes the sodium sulfate from the mix. The sodium carbonate in the black liquor is not changed in the recovery boiler, and simply melts and mixes with the molten sodium sulphide. This mixture forms the smelt which is drawn off the bottom of the recovery boiler into the dissolving tank. Secondary air is added to the furnace above the char bed, and possibly tertiary air above that, to ensure that adequate air is added in the combustion zone, to completely burn the combustible material in the black liquor. The secondary and tertiary air ports also assist in creating turbulence. In the dissolving tank, the molten smelt is dissolved in weak wash from the recaust. This weak wash has also been used to wash lime mud and contains residual white liquor chemicals. The solution formed in the dissolving tank is called green liquor because it gets a greenish color from iron compounds in the liquor. The green liquor is the primary ingredient used to produce white liquor in the recaust. The flow of green liquor from the dissolving tank
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is controlled to maintain green liquor density within required limits. If the green liquor is too weak, the white liquor will be too weak also. The green liquor is drawn off slowly enough, to control the amount of smelt dissolved in the liquor to maintain this density. The flow of weak wash into the dissolving tank is then controlled to maintain the level. The smelt flowing from the recovery boiler is very hot and will burn through steel smelt spouts. To avoid this, the smelt spouts are usually water cooled. The smelt cooling water system is very critical because if it fails, the smelt will burn through the spout and come into contact with the water remaining in the smelt spout. This can result in a disastrous smelt-water explosion. Smelt cooling water systems always have a backup water supply, and are usually gravity fed to avoid failure due to the pump stopping. The smelt does, however, flow into the water (weak wash) in the dissolving tank. If a free flow of smelt is allowed, the smelt-water reaction in the dissolving tank can become dangerous. To avoid this, the smelt flow must be checked and kept steady through all spouts. In addition, the flow is broken up by a jet of steam so that only small droplets of smelt contact the water. This steam jet is called a shatter spray. Often a nozzle using recirculated green liquor is also used below the shatter spray. The green liquor nozzle is sometimes called a fishtail. In addition, the smelt is quickly dissolved by agitators in the dissolving tank. During normal operation a recovery boiler burns only black liquor. However, an auxiliary fuel is required for startup of the boiler and for burning down the char bed when shutting down the boiler. In addition, auxiliary fuel burners are sometimes used to assist in producing steam required for the process, when the power boilers cannot keep up to the demand. Burners may also be required to keep the furnace temperature high enough to ensure good combustion and reduction of the liquor.
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Often two sets of auxiliary fuel burners are used. Load burners are located higher in the furnace, to assist in producing steam and hearth burners are located low in the furnace, to increase the furnace temperature and help burn down the char bed. When shutting down a recovery boiler, it takes several hours to burn down the char bed and then several more hours for the remaining smelt to cool enough, to allow the furnace to be washed out with water.
Chemical Recovery Boiler

Chemical recovery boilers are similar to other large industrial boilers, but have several construction features, to provide safety and stability for the combustion of black liquor and handling of smelt and saltcake.
Figure 17 Chemical Recovery Boiler

50 Supplementary Information Pulp and Paper Mill Operations Unit B1-10 Workbook
This figure shows a modern single drum recovery boiler, which uses strong black liquor from a concentrator (no direct contact evaporators). Notice that the bottom of the furnace is sloped toward the smelt spouts to assist the flow of smelt. The furnace is completely surrounded with tubes like most modern industrial boilers, but the tubes in the lower section around the char bed have short studs, welded to them. Smelt builds up between these studs, and is cooled by the tubes causing this smelt to freeze, forming a refractory type layer on the tubes, which protects them from the erosion and chemical reactions in the char bed area. Note that down comers from the steam drum are located completely outside the boiler. These lead to headers at the bottom, below the furnace floor, which feed the furnace wall tubes. The water and steam flow upward through the wall tubes (risers), rises back to the steam drum where the steam is separated. The steam then passes through two passes in the primary superheater, and then through the secondary superheater before leaving the boiler. Normally, a desuperheater is located between the primary and secondary superheater. This controls the steam temperature, leaving the secondary superheater by spraying water into the steam entering. Cooling the steam before the secondary superheater instead of after, helps to protect the secondary superheater tubes. The flue passes through the superheaters through a convection section boiler bank. After the boiler bank, is a large economizer to lower the flue gas temperature while preheating the feedwater. Older recovery boilers with direct contact evaporators have small economizers, since the gases are cooled in the evaporator. The electrostatic precipitators used on modern recovery boilers are very large. This is to remove the saltcake that tends to be carried over with the flue gases. Since there is no direct contact evaporator to remove these, a larger precipitator is required. The saltcake is mixed back into the black liquor in a mixing tank.
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A lot of the saltcake is removed from the flue gases, as they change direction in the boiler bank and economizers also. The saltcake falls to the bottom hoppers where it is discharged into conveyors and carried to a mix tank. At the mix tank, the saltcake is dissolved in black liquor pumped up from the heavy black liquor storage tank. The induced draft fan is usually located on the outlet of the precipitator to maintain the precipitator below atmospheric pressure and keep saltcake from blowing out openings. This also reduces the saltcake in the flue gases passing through the fan and reduces erosion. The induced draft fan discharges to the stack. Chemical recovery boilers have two different stacks. One for the boiler flue gases and one for the dissolving tank. The molten smelt running into the dissolving tank results in the generation of a considerable amount of steam in the dissolving tank. This steam must be vented to prevent over pressurizing the dissolving tank. The steam carries chemicals, which must be removed before it is vented. This is necessary to reduce pollution and recover the chemicals. A scrubber is used on the dissolving tank vent. The scrubber fan draws vent steam off the main stack and forces it through the scrubber. The steam enters tangentially causing it to swirl around inside the scrubber. This action causes the saltcake particles to be thrown out of the flow. Weak wash is sprayed into the scrubber to dissolve the saltcake and wash it back down to the dissolving tank.
Recaust Flows
The final stage of liquor recovery takes place in the recausticizing plant. Green liquor from the recovery boiler dissolving tank is cleaned to remove carbon and other contaminants from the recovery boiler and then calcium oxide is added to convert the sodium carbonate to sodium hydroxide.
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Figure 18 Recausticizing Plant The green liquor is pumped to the recaust where it enters a clarifier. The clarifier allows heavier suspended matter such as carbon to settle out. The green liquor has a tendency to form crystals which eventually plug up the lines and pumps. To reduce this problem, two green
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liquor lines are used. Weak wash is pumped through one line from recaust back to the recovery boiler. Green liquor is pumped through the other line from the recovery boiler to recaust. The weak wash flushes out the line while the other green liquor line is in service. The lines are switched over daily or whenever plugging problems occur. This keeps the lines clear. The dregs, which settle out in the clarifier are usually washed to remove residual chemicals and then discarded. This is often done in another clarifier called a dregs washer. Water, used to wash the dregs is supplied from the evaporators as contaminated condensate. This recovers chemicals in the dregs and the condensate is then used to wash the lime mud also. After clarifying, the green liquor is pumped to the slaker. In the slaker, calcium oxide (quick lime) is added from the hot lime silo. The calcium oxide reacts with water in the green liquor to form calcium hydroxide. This is called lime slaking. CaO calcium oxide + H2O water Ca(OH) 2 calcium hydroxide
As you know from water treatment, calcium compounds are not very soluble in water and, therefore, the slaker and causticizers contain a slurry of lime mud and liquor. Constant agitation is used to keep the lime mud in suspension. Once the lime is slaked to calcium hydroxide, it begins to react with the sodium carbonate in the green liquor. This reaction forms sodium hydroxide and calcium carbonate. Sodium hydroxide stays in solution but the calcium hydroxide does not. This is a fine powder of limestone in liquor. Limestone is added to make up for losses in the system. Some of these losses result from limestone rock forming in the kiln, which is removed at the slaker and discarded. The waste removed from the slaker is called grits. Na2CO3 + sodium carbonate Ca(OH) 2 Calcium hydroxide 2 NaOH Sodium hydroxide + CaCO3 Calcium carbonate
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The causticizing reaction takes place in the slaker and causticizers, and then the mud solution produced is pumped to the white liquor filter. This is now a solution of white liquor and limestone. In many plants, the limestone mud is separated by settling in a white liquor clarifier. These work fairly well because the limestone is so heavy that it settles rapidly. However, some limestone is carried over with the white liquor. To prevent this carryover, other mills use white liquor filters like those shown in the figure. These may be pressure filters as shown of unpressurized open filters. In either type of white liquor filter, the limestone slurry is pumped into a large vessel and begins settling. The level rises in the vessel as the slurry is pumped in. Filter socks extend down through a separator plate near the top. The white liquor must pass through the filter socks so that lime carried with the liquor is filtered out. The filtered white liquor then goes to the storage tank before being pumped back to the digesters for re-use. In pressurized units, the vessel is closed and as the level rises, air trapped above the white liquor outlet is compressed in the top, providing a slight pressure in the vessel. In others, the top is open to atmosphere allowing the air to escape and is not under pressure. The flow through the mud filter is stopped every few minutes for a short period. This is done by shutting off the liquor flow into the filter. Stopping the flow allows white liquor above the separator plate to run backward through the filters, and dislodge the lime building up. In a pressure filter, this is assisted by the air pocket which expands in the top of the filter. The mud removed from the filter socks is allowed a short settling time, before the flow is started again. Mud settles to the bottom of the liquor filter and is scraped out by a slowly rotating rake assembly. The mud is filter mixed with condensate and pumped to a second filter (or clarifier). The condensate washes residual white liquor chemicals off the mud. The weak wash produced is then recovered and used to produce green liquor at the recovery boiler as described earlier.
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The lime mud, like the liquor chemicals, is re-used over and over. Once washed, the mud is pumped to a mud filter where the water is removed forming a mud cake. This mud cake then goes through a lime kiln. The kiln is a long steel tube which is lined with refractory. The kiln rotates slowly and is fired at the bottom using an auxiliary fuel burner. The incline and rotary motion of the kiln causes the lime mud to cascade around the sides of the kiln and slowly move down the kiln from the mud filter toward the kiln burner. As the lime mud passes through the kiln it is heated. The hot gases evaporate the remaining water from the lime mud. Once the water is evaporated, the dry lime mud (calcium carbonate) is heated. Heating the lime mud results in a chemical reaction, that breaks down the limestone driving off carbon dioxide. This converts the calcium carbonate into calcium oxide (quick lime). The dry quick lime is then transferred to the hot lime silo where it is stored until required for re-use in the slaker. CaCO3 calcium oxide + CaO calcium oxide + Ca(OH) 2 carbon dioxide
Recovery Boiler and Recaust Hazards

There are several hazards involved with chemical recovery in a Kraft paper mill. First of all, are the typical hazards of working around the boilers which include burns from hot steam, fuel and water lines, hazards of furnace and boiler explosions, electrical shock hazards, fall hazards etc. In addition to this, two hazards are especially applicable to recovery boilers. These are: smelt-water reactions chemical burn hazards
As mentioned earlier, smelt-water reactions occur in and around the chemical recovery boiler when water comes into contact with hot smelt. Since water can be leaked into the boiler, if the liquor solids concentration becomes too low or when a tube leak occurs, these possibilities must be
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monitored continuously and when suspected, appropriate action must be taken. Low liquor solids requires diverting the liquor from the recovery boiler. Leaking from boiler furnace tubes can be catastrophic. This must be monitored by all personnel in the recovery boiler department. If leaking is suspected by any personnel, the lead operator must be informed and if it is determined that the possibility of a smelt-water reaction exists, emergency procedures must be initiated. This consists of carrying out an emergency shutdown procedure. (ESP the boiler) When a tube leak occurs, the recovery boiler is shut down immediately. However, since it takes several hours to stop the smelt from forming at the char bed, the boiler must be drained to stop water from leaking from the tubes. An emergency shutdown procedure is normally initiated by pressing a button in the control room. When the button is pressed the procedure is carried out automatically. This involves shutting off all the fuel to the boiler and opening rapid drain valves. The pressure in the boiler quickly forces the water from the boiler to the ESP blowdown tank. Once the boiler is drained, the vent is opened to release any remaining pressure to atmosphere. The rapid drain valves are special motorized valves used on recovery boilers. These are located about 8 feet from the bottom of the recovery boiler furnace floor. The valves open and drain the water down to this level. Some water is left in the bottom of the furnace tubes around the char bed, to minimize damage to the boiler tubes due to overheating. With the pressure released, little water will leak even if it is below this level. When a rapid drain is initiated, it also sounds alarms and starts lights flashing in the recovery boiler area. This is a sign for all personnel in the area to exit immediately, and for no one to enter the area during this time. The rapid drain valves and system must be tested on a regular basis. Manual valves at each rapid drain valve can be closed, when testing the rapid drain valves for operation. These manual valves must be locked in the open position when not testing the rapid drain valves.
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The main chemical concern around Kraft recovery boilers and recaust equipment is due to caustic soda (sodium hydroxide). All liquors have caustic soda to some degree. White liquor is the most hazardous due to its high caustic content. Caustic soda is a strong base which attacks organic matter very quickly. If you come into contact with caustic containing liquids, it causes a slippery sensation on the skin. The affected area must be washed immediately with large quantities of water until the slippery sensation is gone. If further irritation occurs, medical professionals must be consulted. Caustic soda in the eyes will result in rapid clouding of the surface of the eye resulting in blindness. Always wear full face protection when working around caustic soda and Kraft liquors. Refer to the MSDS for caustic and other chemicals used in the recovery boiler and recaust area.
Alternative Chemical Recovery Process

Due to the hazards of smelt-water reactions that occur in the recovery boilers, much research has gone into developing alternative methods of recovering pulping chemicals. Although no major installations have been installed in Canada, some pilot plants and one full scale plant have been built using steam reformer technology. Since this process is still in the development and research stages, little information is available at this time but it involves the use of fluid bed technology and heating the liquor without direct flame contact. As a result, the liquor is vaporized leaving the chemicals behind as a solid mixed into the fluidized bed. The vaporized organic material (lignin) from the reformer furnace is scrubbed and then burned in separate boilers as a gaseous fuel. In this way, no smelt bed is formed and the risk of a smelt-water reaction is eliminated.
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1. Explain why the black liquor entering the recovery must have a high solids concentration.
2. Describe what actions must be taken when a tube leak is suspected in the furnace of a black liquor recovery boiler.
3. Write, using symbols and words, the equation that represents the chemical reduction reaction that occurs in the recovery boiler furnace.
4. State the approximate solids concentration of: weak black liquor strong black liquor heavy black liquor
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5. Explain why direct contact evaporators are no longer installed on new recovery boilers.
6. Write, using symbols and words, the equation that represents the slaking of quick lime in the recaust slaker.
7. Write, using symbols and words, the equation that represents the recausticizing reaction in the causticizers.
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8. Write, using symbols and words, the equation that takes place in the lime kiln as the calcium carbonate is converted to hot lime.
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