Chapter 1: General Characteristics of Kraft Black Liquor Recovery Boilers 3 CHAPTER 1 General Characteristics of Kraft Black Liquor Recovery Boilers Dr. Terry N. Adams Technical Consultant, Tacoma, WA, USA 1.1. INTRODUCTION Black liquor is the by-product of chemical pulping. It contains almost all of the inorganic cooking chemicals along with the lignin and other organic matter separated from the wood during pulping in the digester. The initial concentration of weak black liquor is about 15% dry solids in water. It is concentrated to firing conditions between 65% and 85% dry solids content in the evaporation plant or a combination of the evaporation plant and a direct contact evaporator, It is then burned in large units called black liquor recovery boilers The ewo main functions of recovery boilers are to recover the inorganic cook- ing chemicals used in the pulping process and to make use of the chemical energy in the organic portion of the liquor to gen- erate steam for the mill. The ewin objec- tives of recovering both chemicals and energy make recovery boiler design and operation more complex than virtually any other boiler application. ‘The organic and inorganic material in the black liquor are intimately mixed Combustion in the furnace converts the organic material into gaseous products in a series of processes involving drying, devolatilizing (or pyrolyzing), char gasifi- ‘ation, and finally homogeneous combus- tion in the furnace volume. Burning of the solid char, the residue left after pyrol- ysis of the black liquor, occurs largely on the char bed which covers the floor of the furnace, though some char burning ‘occurs in flight. As the carbon in the char is gasified, the inorganic compounds in the char are released and form a molten salt mixture called smelt, which flows to the bottom of the char bed and is tapped from the furnace through smele spouts. The molten stream of smelt leaving the spouts is shattered by jets of steam, and sometimes also green liquor, as it falls into the dissolving tank, where it dissolves in weak white liquor from the lime mud wash- ing process. This produces the raw green liquor which reurns to the recausticizing plant for clarification and causticizing, The smelt from a kraft recovery boiler consists of approximately two-thirds Na,CO, and one-third Na,S, with small amounts of Na,SO,, other sodium/sulfur compounds, arid unburned carbon. It is the NaS used in the kraft pulping process which “adds to the complexity of the recovery process. Production of Na,$ in the furnace instead of NaSO,, of any other partially oxidized sodium/sulfur compound, requires both a reducing ent and a physical layout which limits the contact of the smelt with air. At the same time, the organic portion of the Black liquor can only be Rilly consumed and converted to useful energy by intense mixing and combustion with air (or more precisely, oxygen). Modern recovery boil- er design accomplishes these two objec- tives toa remarkable degree. Descriptions of the recovery proceses and boiler operating strategy vary, but there ae two features Which are universal ly agreed upon I. Water from any source must not con- tact the char bed. There is a well-doc- umented, violently explosive reaction becween water and smelt. The reac~ tion is physical in nature and involves vety rapid generation of vapor from water due to contact with hot smelt. ‘The volume expansion of water as it4 Kraft Recovery Boilers Figure 1-1, General arrangement of a kraft recovery boiler system. vaporizes pushes the surrounding furnace gas away so rapidly thar a highly destructive detonation wave is generated. Contact of water with smelt can cause massive damage to the boiler. Ul. Wet black liquor must not reach the char bed. Black liquor from the con- centrator, or direct contact evapora- tor, cont between 15% and 40% water. If this water reaches the char bed there is risk of a smele-water explosion, particularly wich liquor dry solids below 58%. Aside from the risk of smele-wacer contact, wet black liquor reaching the bed causes local blackout of a portion of the bed sur- face. Because liquor must be dry and hot to bum, the bed will noc resume burning until heat from the bed, oraches the char a smelt-water y with liquor Aside from the tact, wet black ed causes local ofthe bed sur- ust be dry and ill not resume m the bed, or Chapter 1: General Characteristics of Kraft Black Liquor Recovery Boilers 5 Figure 1-2. Schematic diagram of a two-drum recovery boil Stack gas Feedvater Steam to mill ing steam Indeed rat fan | Weteral Electrostatic te precintator fan | Gee Seament ‘airheater 000 0 0-f—+ tertiary air Strong black quer Secondary ar Make-up chemicals Primary a eters tN. from the combustion above the bed, dries and pyrolyzes the wet liquor. Pee ees 0s ee the bed depends in part on the tem- perature ofthese gases leaving the red, so the two processes are interde- pendent. Wer black liquor reaching the bed. in sufficient quantity can break this feedback and cause a gen- eral blackout of the furnace. In this situation, pyrolysis of the blacle liquor can continue due to the heat stored in the bed, filling the furnace with combustible gas. A serious com- bustible gas explosion hazard can exist until stable ignition is reestablished. The above two safety-related issues will be covered in detail in Chapter 11 of this book. The purpose of this chapter is to describe the general features of recov- Smelt dissolving tank SMe sP0us exy boilers. It is broken into sections which deal with: 1) recovery boiler equip- ment, 2) material and energy balances and, 3) general combustion calculations. The equipment section will provide a general description of recovery equipment and identify major differences in the designs offered by various vendors. A more detailed description of this equip- ‘ment can be found in reference [1] which also presents generalized operating and emergency procedures. 1.2. RECOVERY BOILER EQUIPMENT 1.2.1 General Layout Figure 1-1 shows the general layout and equipment for a recovery boiler sys- tem. Toward the front in the figure is a set6 Kraft Recovery Boilers Figure 1-3, Side elevation of a singledrum recovery boiler. of evaporators for increasing the concen: tration of the weak black liquor from about 15% dry solids to the firing dry solids level between 65% and 85%. The recovery boiler itself is suspended in the middle of the support structure which also houses the fans, tanks, and other aux- iliary equipment. Behind the recovery boiler in Figure 1-1 is the electrostatic precipitator. A schematic diagram of a recovery boiler system with a ewo-drum boiler is shown in Figure 1-2. Figure 1-3 shows a side elevation of a modern single-drum recovery boiler. The general layout andhe electrostatic of a recover drum boiler & re 1-3 shows a in. single-drum ral layout and Chapter 1: General Characteristics of Kraft Black Liquor Recovery Boilers 7 Figure 1-4. Lower furnace arrangement of a recovery boil q | nose aeh i “Todiary aleve! So Primary Dust from preciptator « Secondary airlvel aL nozzte vel a ar seers: ee Primary ai lovel " oportioning shown in these figures are Eortect for most modern recovery boilers. Recovery boilers have two main sections: a furnace section and a convective heat transfer section. All mixing and combus- tion of the fuel and air should be com- pleted in the furnace section. About 40% of the heat transfer from the combustion gas is completed in the furnace. Heat transfer co the boiler water to form high =O Main eisolving tank wi agitators pressure steam is then completed in the convective heat transfer section. The nose arch or bullnose shown in Figures 1-2 and 1-3 is the general demarcation between these two sections. Many of the features in the upper part and back end of the recovery boiler are enerally similar to other types of boilers. The upper pare of the boiler contains four sets of tube banks: the screen tubes which8 Kraft Recovery Boilers slightly cool the upward flowing combus- tion gas fom the furnace before they enter the superheater, the superheater which increases the steam temperature from saturation to the final superheat temperature, the boiler bank (or steam generating bank) which, along with the Furnace walls, is where water is evaporat- ed to steam, and the economizer at the back where the feedwater temperature is raised to just below ies boiling point before ic enters the boiler drum. The lay- out of the convective sections generally involves countercurrent flow of combus- tion gas and boiler water, though parts of the superheater may be co-current. The tube layout and orientation in the indi- vidual sections can result in either cross flow or parallel flow heat transfer. Figure 1-4 shows a more detailed view of a recovery boiler lower furnace. The three air levels are shown along with the location of the black liquor guns and the smelt spouts near the bottom of the furnace. Ports must be provided in the lower furnace for introduction of air, liquor gunsy and other openings such a fs fuel burners, entry doors, and inspection ports. These penetrations are formed by bending one or several wall tubes either directly to the side or by bending them ‘out of the plane of the tube rows and to the side, on the outside of the furnace. Because tubes must be bent to form pen- ettations of the waterwalls, itis common practice to use ports in the shape of ver- tical slots so that a given port area can be obtained with the minimum number of tube bends Before going to the furnace, the black liquor “fuel” may be modified by the addition of several different types of material. A variety of makeup chemicals may be added including purchased salt- cake (Na,SO,), saleeake from CIO, gen eration, elemental sulfur, or other sodi- um and sulfur-rich materials. Also, there is a very substantial amount of particu- late from the boiler and economizer hop- Figure 1-5. Arrangement of a black liquor gun, port opening, and liquor spray. Furnace waterwall pers and the electrostatic precipitator that is recycled to the furnace by adding it into the black liquor. This material can be added either in a mix tank or, in units having a direct contact evaporator (DCE), a portion of the recycle material may be added there. This mixed fuel is heated in the mix tank and in separate heaters, which can be either indirect con- tact of direct contact with steam, in order to reduce the liquor’s viscosity and con- trol its spray characteristics. The resulting “asefired” fuel is sprayed into the furnace through a set of liquor guns which have specially designed nozzles at their tips. 1.2.2 Liquor Guns ‘The liquor gun ports are located at an elevation in the furnace of about 5 m (15 f) above the floor of the furnace. Depending on boiler manufacturer and load, between one and sixteen liquor guns are used to fire the boiler. Figure 1-5 shows a liquor gun mounted in a liquorfa black ind liquor Black liquor ecipitator that by adding it naterial can be k of, in units € evaporator cycle material mixed fuel is id in separate rindirect con- ream, in order sity and con- The resulting co the furnace 1s which have c their tips. - located at an bout 5 m (15 the furnace. ufacturer and en liquor guns Figure 1-5 ed in a liquor Chapter 1: ort spraying black liquor into the fur- hace. There ipa liquor nozae atthe end of the gun which spreads the liquor out so it covers more of the furnace cross-sec- tion. The particular nozzle shown in Figure 1-5 is a splashplate nozzle which produces a flat fan spray of black liquor. The splashplate nozzle is the most common type of black liquor nozzle, I is designed so that the black liquor stream impinges on a flat plate after it leaves the nozzle. The flat plate is fixed to the out- side of the nozzle at an angle between 35° and 52° to the flow. The impinging stream of black liquor forms a wide, flat sheet of droplets. The combination of gun angle and splashplate angle deter mine the initial trajectory of the liquor into the furnace and governs the contact bevween the liquor and the combustion air. Another type of black liquor nozzle is the conical spray nozzle. A spiral grooved block is inserted at the inlet to the nozzle to produce a swirling motion of the black liquor which then leaves the circular noz- ale exit as a conical sheet. Another ater- native nozzle is one with an lliptica mouth. Another nozzle uses a tangential liquor entry into the nozzle to produce a swirling motion. The liquor exits the nozzle axially through a circular opening to produce a conical spray pattern. There are substantial differences in the design of the nozzles offered by vari- ous vendors, but the common feature is that they all produce a fairly coarse spray, xypically from 0.5 to 5 mm droplet size. ‘This isan order-of-magnitude larger than other fuel sprays. The coarse spray mini- mizes entrainment as the droplets fall through the upward flowing furnace gases. The black liquor droplets. have time to dry and partially pyrolyze during their flight down from the nozzles to the bed. The material reaching the bed con- sists of a combination of the inorganic material, a portion of the volatile organic material, and the solid residual char from neral Characteristics of Kraft Black Liquor Recovery Boilers 9 the organic pyrolysis. For the portion of the liquor droplets that avoid entrain ment, pyrolysis is completed on the hot char bed. Black liquor spraying is covered in more detail in Chapter 4. 1.2.3 Combustion Air System ‘Combustion air is delivered to the fur- nace through a series of ducts and wind- boxes attached to the boiler. The air flow is directed into the furnace through air ports. The air flow rate is controlled by dampers that can be located in the ports, the windboxes, the ducts, or atthe forced draft fan. The ports are laid out in hori- zontal rows located at several elevations up the furnace. Shown in Figure 1-4 is a three-level air system consisting of prima- ry air located approximately 1 m (3 fi) above the furnace floor, secondary air located at approximately 2 m (6 fe) above the floor, and tertiary air located above the liquor guns approximately 8 m (25 i) above the floor. Primary and secondary air ports are nearly always distributed on all four walls of che furnace. Tertiary ports are usually located only on ewo opposing walls. ‘Typically 65% to 85% of the combus- tion air is introduced below the liquor guns, generally in the region of the char bed.’ The air in the lower furnace impinges on the char bed, burning the solid carbon to CO or CO, as well as burning the remaining pyrolysis gases. Combustion of the pyrolysis gas and the sified carbon in the tegon above the Bed provides the hea char melts the inor- gens ‘compounds and reduces Na,SO, to Na,S, thus forming the smelt The primary air ports are always the smallest and most numerous. On a recov- exy boiler designed for a 1000 TPD mill, approximately 35 primary air ports will be located on each of the four walls. The size of these ports is approximately 5 by 25 cm (2 by 10 in.). Primary air is used to control the shape and position of the perimeter of the char bed and to provide10 Kraft Recovery Boilers Figure 1-6, Two arrangements for the secondary level of a recovery boiler. VV VV AAAAAASL t+ A 4 * 4 4 Pian View of 4-wall Secondary Air a portion of the air for char combustion, Windbox pressures of 0.5 to 1.0 kPa (2 to 4 in, of H,O) are typical for the primary air. The secondary air ports are generally larger and less numerous than the prima- ry ports. There can be from 4 to 16 ports ‘on each wall of the furnace ranging in size from 5 by 25 cm (2 by 10 in.) to 12.5 by 67.5 cm (5 by 27 in.). Windbox pressures from 1 to 3 kPa (4 to 12 in. of H,O) are gypical for the secondary air. The sec- “ondary air controls the position of the top of the bed and burns the pyrolysis gas and CO from the bed. The tertiary air ports are the largest air ports. They are usually located on the Font and’ rear walls Typically from 3 to 8 tertiary ports are used on both walls and these are between 10 by 45 cm (4 by 18 in.) and 15 by 75, cm (6 by 30 in.) in size. Air pressures between 1.25 and 5 kPa (5 and 20 in. of H,O) are typical for the tertiary ait. The tertiary air provides air to complete the combustion process and the final mixing of the combustion gases. The number and size of ports at each level is deter- mined by the desired liquor burning capacity, the air pressure available, an the air split between the levels selected by the manufacturer t—t—+—+——+ Plan View of 2-wall Secondary Air This general layout for the three-level air delivery system is nearly standard for all five major recovery boiler vendors in North America, though details of the design vary considerably among them. The major exception to this pattern of air ports is the design of Combustion Engineering (now ABBCE) recovery boil- ers built prior to the early 1980's, which use only two levels of air. The lowest level is called the primary air and is very simi- Jar in location, size, and number to the three-level air’ system described above. Generally there is somewhat more open port area in the primary level of a swo- level system compared to the primaries of a three-level system for the same liquor firing capacity. The other level of air in a eworlevel system is located above the liquor guns. Although this level of air has been referred to as secondary air, current ly accepted nomenclature identifies sec- ondary air as being below the liquor guns and identifies tertary ait as belng above the guns. The upper level of air in the two level system introduced tangential ly by placing one large nozzle on each of the four walls. Each nozzle is located at a point one-third of the distance from the right hand corner of the wall or at each corner. The air jets are directed inwardoiler. ry Air che three-level y standard for let vendors in details of the among them s pattern of air Combustion recovery boil- 1980's, which he lowest level d is very simi- umber to the ctibed above at more open crcl of a two. 2¢ primaries of e tame liquor evel of air in a ed above the level of air has ry ait, current identifies sec- he liquor guns ss being above [of air in the ced tangential- ale on each of is located at a ance from the vall or at each irected inward Chapter 1: General Characteristics of Kraft Black Liquor Recovery Boilers 11 Figure 1-7, Two arrangements for the tertiary air level of a recovery boiler. Plan View of Concentric Tertiary Air along the tangent to an imaginary firing circle centered on the vertical centerline of the furnace producing a strong rotat- ing flow of the combustion gases as they Some furnaces are now being built or modified to have four levels of air. The fourth level is usually above the liquor guns and is called quaternary air. The main purpose of this level is for added flexibility in air distributions which can be used to control the level of some air emissions, Figure 1-6 shows two of the many possible layouts for the secondary air ports. The arrangement on the left is a conventional four-wall secondary arrangement. The arrangement on the right is a two-wall secondary system intended to provide becter mixing by par- tially interlacing the secondary air jets through the use of alternating large and small air nozzles. The number, size, and spacing of the secondaries varies from vendor to vendor. Figure 1-7 shows two layouts for the tertiary air jets. A tangential arrange- * Plan View of Interlaced Tertiary Air ment is on the left and a two-wall inter- laced arrangement is on the right. Recovery boiler air systems are covered in more detail in Chapter 7. 1.2.4 The Char Bed and ‘Smelt Spouts Figure 1-8 shows a cutaway view of the lower furnace of a flat boomed recovery boiler. The liquor sprays are not shown, but the primary and secondary ait jets and the smele flow out of the smelt spouts is shown, A rather substantial char bed covets or displaces a portion of the smelt pool in this flat bottomed decanti- ng hearth furnace. The top of the char bed is typically at about the elevation of the secondary air jets, chough much larg- er and much smaller beds are also observed in different boilers, or in the same boiler under different operating conditions. The smelt spouts are located below the primary air ports. In sloped floor designs, the smelt spouts are located on the wall adjacent to the lowest point of the floor. The smelt flows by gravity to the spouts. In flat floor units, pores for12 Kraft Recovery Boilers Figure 1-8. Sketch of the lower furnace of a flat bottomed recovery furnace. (3 Composite Tubing BEB Carbon Stoe! Tubing Clad bar fin Stainless steo! Carbon steel ‘Composite Tubingace, suction, fin Chapter 1: General Characteristics of Kraft Black Liquor Recovery Boilers 13 Figure 1-10. Arrangement of two super- heater platens. the smelt spouts. are located on one or both side walls approximately 0.5 m (1.6 8) above the floor level. A pool of molten smelt forms in these units and decants out through the smelt spout openings. Char beds are covered in more detail in Chapter 6. 1.2.5 Lower Furnace Construction Figure 1-9 shows the general configu- ration of the walls in the lower furnace, ‘The furnace walls are constructed of ver- tical tubes set in a row. These tubes are typically 6.4 to 7.6 em (2.5 to 3 in.) in diameter, In modern construction they are usually spaced approximately 1.25 t0 2.5 cm (0.5 to 1 in) apa, connected by a flat fin. The fin is continuously welded along the line of contact between the fin and the tube making a gas-tight enclo- sure. This is referred to as membrane con- struction. In some older units the fins are not connected in the center between tubes, so a packing is used on the cold side of the furnace walls to provide a near- ly gas-tight arrangement. In some other boilers no bar is used and the tubes are directly welded to each other. This is referred to as tangent construction. The rows of bes which form the four furnace walls are connected to headers which are part of the water circulation circuit for the boiler, and so are called waterwalls. Water rising in these wall tubes receives heat by radiation from the char bed and flames in the furnace. The furnace walls can repre- sent as much as one half of the heat trans- fer surface required to produce high pres- sure steam. Figure 1-9 also shows one of the meth- ods of fabricating the tubes to male them more resistant to corrosion. The tubes are made with a stainless steel sheath on the outside of a carbon steel tube. This is called a composite tube. Another way of rotecting the tubes from corrosion is to — bed of a chrome-based material. Some of the chrome diffuses into the carbon steel making the outside surface resistant t0 corrosion. This treatment is called chromizing. Corrosion in recovery boilers is covered in more derail in Chapter 10. 1.2.6 Convective Heat Transfer Section In the upper furnace, the nose arch or bullnose is located on the rear wall of the furnace. Its purpose is to protect the supetheater from direct furnace radiation and to help urn the upward flowing com- bustion gas around the corner toward the boiler exit opening in such a way os to proce tnifocm How over the heat trans. The convective heat transfer section consists of the supetheater, boiler bank, and economizer, and may include a set of screen tubes. Heat transfer from the gas to these tube banks is largely by convection,14 Kraft Recovery Boilers bur radiation can contribute nearly half the heat transfer in the hottest part of this section. In lower pressure designs, screen tubes are placed in front of the super- heater section. The boiler bank is always a bank of in-line tubes, typically 6.4 cm (2.5 in.) diameter on approximately 11.4 cm (4.5 in,) side spacing. Greater spacing is often used for the front several rows of tubes to reduce plugging of the flow pas- sages. The supetheater can either be a bank of in-line tubes with side spacing of approximately 30 cm (12 in,) or can be Dlatens also on wide side spacing Patens are supetheater tube sheets with in-line tubes of zero front-to-back spacing, Figure 1-10 shows two supetheater platens. The superheater tubes are gener- ally laid out in this flac platen arrange- es er ee a are spaced across the furnace width above the nose arch elevation. This flat, parallel arrangement establishes the flow paths for the combustion gas. It provides room for deposit buildup on the superheater platens, which is a chronic operating fea- ture of all kraft recovery boilers, The flat arrangement also provides a geomet from which the deposits are more easily removed by the soorblowers. Figure 1-11 shows both a plan view” and a side elevation of the boiler bank and the nearest set of superheater platens. The platen arrangement is shown for the supetheater and the typical in-line tube arrangement is shown for the boiler bank. One obvious thing here is that the boiler bank tubes are more closely spaced than the supetheater tubes. This is neces- sary to get enough heat transfer surface area packed into a limited space. The boiler bank tube spacing is a tradeoff between its tolerance for plugging and the cost of the boiler. However, this is a key geometric feature which plays an important role in boiler bank pluggage with fume and carryover deposits Cleaning the tightly spaced boiler bank passages is more dificule than for the superheater passages. Deposits and plug. Figure 1-11, Tube spacing in the boiler bank. 000 000000; 000 22mm) 000 000000! 000: 000000 ging in the convective section of a recov- ery boiler is covered in more detail in Chapter 9. Economizers consist of many small tubes in tight bundles in order to provide enough surface area for heat transfer between the low temperature combustion gas entering the economizer and the water flowing in the tubes. Many recovery boilers have screen tubes in front of the superheater tubes Screen tubes are usually, but not always, water-filled cubes which are part of the boiling heat transfer circuit. Their pur- pose is to cool the combustion gases somewhat before they enter the super- heater section, to block radiation from the furnace to the superheater tubes, and to collect some of the particulate carry- over from the furnace. 1.2.7 Sootblowers Tubes in the superheater and boiler bank sections are widely spaced to accom- modate the substantial carryover of solid particulate from the furnace. Carryover, along with the high temperatures in this region, causes continuous deposition and fouling on the outside off the tubes. Though automatic, retractable sootblow-in the boiler 3 60 00000 60 000000 60 0000007 00 zomm (en 00 000000 007 115 mms) 20! 000000 Section AA dion of a recov- more detail in of many small der to provide heat transfer 1re combustion nizer and the ach s have screen echeater tubes, Dut not always, are part of the uit. Their pur- nbustion gases iter the super | radiation from ater tubes, and | rticulate carry- wer and boiler ced to accom. ryover of solid ace. Carryover, eratures in this deposition and ei the tubes. able sootblow- Chapter 1: General Characteristics of Kraft Black Liquor Recovery Boilers 15 Figure 1-12. Sketch of a sootblower cleaning a tube bank. ing lances are always used with recovery boilers, substantial fouling of che surfaces still occurs, and complete pluggage of the gas flow passages is an all-too-common problem with units operated near ot above their design rating. Fouling ten- dency must be accounted for in deter- mining the amount of heat transfer sur- face area needed for cach step of the steam raising process. The amount of hheat transfer surface area required in a kraft recovery boiler would be sufficient to generate twice.as much steam with a non-fouling fuel Figure 1-12 shows a soot blower par- tially extended ino a tube bank. The high pressure steam jets issue from two ‘opposed nozzles on either side of the lance tube near the tip. The steam jets knock deposits off the boiler banle and supetheater tubes. Soot blowers are locat- ed in every section of the tube banks and are operated in a continuous sequence in order to keep the deposits from bridging and plugging the boiler. By periodically removing the cube deposits, the heat transfer between the combustion gas and the tubes is maximized. 1.2.8 Recovery Boiler Capacity Rating The size of the furnace and the amount of heat transfer surface area are dependent on the desired liquor firing capacity. Each boiler is rated both in terms of its capacity to process black liquor solids from the pulping operation and its capacity to raise steam for the mill, Ratings can vary considerably depending on the analysis of the black liquor, liquor sulfidity, organic/inorganic ratio and other factors. Te is common practice to rate a recovery boiler in terms of the daily pulp production it must han-16 Kraft Recovery Boilers Table 1-1, Sample analysis of kraft black liquor (concentrator product). 8 D 5 Element wt% BLS 6 carbon c 35.0% 7: hydrogen H 3.3% 8 oxygen ° 35.7% 9 sodium a i 19.7% 10 potassium K 1.6% 11 sulfur Sulfur 40% 12 chloride a 0.6% 13 inerts Si, Al, Fe, Ca, etc 0.1% 14 Solids s 70.0% 15 Higher heating value HHV 13,950 ki/kg BLS 6,000 Btuylb BLS 16 Net heating value NHV 12,093 kj/kg BLS 5,201 Btu/lb BLS 17 Assumed reduction 90% dle for the mill. A 1000 TPD recovery boiler generally would be able to process the liquor resulting from the production of 1000 tons of pulp per day. A typical average for the weight ratio of black liquor solids to unbleached pulp is 1.5:1, so that a 1000 TPD recovery boiler would nominally handle 3.0. million pounds (1.36 million kg) of black liquor solids per day. The actual rating on a given liquor can vary considerably from this. The design procedures for recovery boilers are covered in more detail in Chapter 12. 1.3. MATERIAL AND ENERGY BALANCE 1.3.1. Material and Energy Balance Boundary ‘The material and energy balances for a kerafe recovery boiler are quite complex because of the multipliciey of input and output streams, the chemical conversions which occur within these units, and the inconsistency in the methods for measur ing and reporting various parameters Selection of the boundary for the materi- al and energy balance is important and the method used in the example present- ed below will generally follow that of the ‘TAPPI Short Form (2). However, some of the minor flows will be directly evaluated in the example in order to make use of certain results in the following discussion. The boundary for the material and ener- gy balance includes the recovery boiler and economizer, the saltcake mix tank, and the direct liquor heater. It does not include che electrostatic precipitator, the ID and ED fans, the evaporation plant, or the steam coil air heater. The black liquor is assumed to come from a concentrator, so a cascade or cyclone evaporator is also not included in the example. The method for handling a material and energy bal ance for a boiler fited with a direct con- tact evaporator is covered in the TAPPT Shore Form. 1.3.2. Black Liquor Fuel Analysis Table 1-1 presents a sample analysis for kraft black liquor. In this and the fol- lowing tables, purchased saltcake will beki/kg BLS. Btu/lb BLS Ki/kg BLS Btu/Ib BLS us parameters, for the materi- imporcane and xample present- low that of the owever, some of rectly evaluated ro make use of ving discussion. terial and ener recovery boiler cake mix tank, ter. It does not >recipitator, the ration plant, or rhe black liquor a concentrator, aporator is also le. The method ind. energy bal- th a direct con- 1 in the TAPPI | Analysis mple analysis his and the fol- saltcake will be Chapter 1: General Characteristics of Kraft Black Liquor Recovery Boilers 17 Table 1-2. Sample analysis of makeup saltcake, J K _ 5 Element wi% 6 sodium Na 32.4% 7 sulfur Sulfur 22.4% 8 oxygen One 4ie% 9 chloride a 03% 10 inert Si,Al Fe, 0.1% Ca, etc, used as the makeup chemical, though other makeup chemicals are often used. A sample analysis of makeup saltcake is pre- sented in Table 1-2. The analysis includes the major species C, H, O, Na, and Sulfur which make up black liquor, along with two other minor species K and Cl which are important for the discussion of fouling and- plugging. Both of these analyses are typical of aft recovery oper= ations, but very substantial variations in liquor analysis do occur from mill to mill and for any one mill over time. Not shown is the concentration of nitrogen in the liquor which is typically near 0.1%. jogen plays a major role in the formas tion of the oxides of nitrogen which are air pollutants in the stack gas, ‘The higher heating value (HHV) for the sample black liquor is listed in Table 1-1. The HHV for solid or liquid fuels is measured in an oxygen bomb calorimeter. This device is a closed container which uses a large excess of oxygen at high pres- sure to ensure that complete combustion is achieved. In -addition, the energy released is measured afterall che combus- tion products are brought back to a tem- perature of 25°C (77°F). The method is accurate, but not completely representa- tive in two importane ways. In most prac- tical combustion processes, the water, which is generated from the combustion of the hydrogen contained in the fuel, leaves the combustion device in the vapor state, In the oxygen bomb calorimeter the water mostly ends up in the liquid state so that its latent heat contributes to the mea- sured HHY, but is not really available in most practical situations. Secondly, any sulfur in the fuel is completely oxidized in the oxygen bomb calorimeter, whereas with kak black liquor ic alwaye appears NaS. In the kraft recovery furnace one of the critically imporcant steps in the process is the production of smefe with high reduc- tion efficiency, ie. a large amount of Na,$ and litde Na,SO,. This reduction process is endothermic by 12,900 kJ/kg of Na,S (5,548 Beu/lb of Na,S}. The oxida- tion of Na,S to Na,SO, contributes to the HHV measured by the calorimeter, but is not an energy quantity available in the actual furnace. Both the hydrogen correc- tion and the sulfur correction are directly handled by loss terms in the energy bal. ance presented later. However, they can also be used to ee the measured heat- ing value to produce a value more repre- ee en er etre black liquor solids. This calculated num- ber is the Net Heating Value (NHV) often referred to as Net Calorific Value (NCV) or the Lower Heating Value (LHV). The NCV is very commonly used. outside North America, An expression for calculating NHV is given below and the value of NHV is presented in Table 1-1 along with the liquor analysis, [Zesutie (nan) an where: NHV = net heating value of BLS, Jkg18 Kraft Recovery Boilers Table 1-3. Sample operating parameters for material and energy balance. ° P Q R s oT 5 Item Metric Units Eng. Units 6 Air excess forced draft (FD) air 6% _of stoichiometric | 7 infiltration air 9% of stoichiometric 8 total excess ait 15% _ of stoichiometric 9 ambient temperature 27 °C 81 °F 10 humility in air 0.013 kg H,O/kg dry air | W FD air preheat temperature 150 °C ca a 42. Black concentrator product solids 70% | 13 liquor concentrator product temp. 108 °C 226 °F 14 saltcake makeup rate 3.0% wt. of BLS 5 direct heating steam for liquor 1.7% wt. of wet BL | 16 dust recycle. 10.0% wt. of initial Na 17 Smelt smelt reduction efficiency 90.0% 18 organic carbon in smelt 1.0% wt of smelt 19 smelt temperature 350 °C 1562 °F 20 smelt enthalpy 1350 ki/kg 581 Btu/lb 21 Stack economizer exit gas temp. 210 °C 410 °F | 22 gas total reduced sulfur as H,S 15 pomw dry flue gas | 23 so, 75 ppmw dry flue gas | 24 co 200. ppmv dry flue gas 25 H, 200 ppmv dry flue gas 26 particulate loading 0.1 g/DSCM 0.044 gr/DSCF 27 Na,SO, in stack particulate 80.0% wt-as Na,SO, 28 NaiCO, in stack particulate 8.0% wt. as Na,CO, | 29 K.SO, in stack particulate 7.3% wt.as K,SO, i 30 KCO, in stack particulate. 0.7% wt-as K,CO, 31 NaCl in stack particulate 4.0% wt as NaCl 32 Na wt% in particulate 31.0% 33, Sulfur wt% in particulate 19.4% 34 Steam blowdown flow 11.0% of BLS 35 circuit sootblowing steam 18.0% of BLS 36 feedwater temperature 110 °C 230 °F 37 steam temperature 482°C 900 °F 38 ‘steam pressure 62.25 bar 900 psig 39 enthalpy of steam 3372 ki/kg 1450 Btu/lbm 40. Misc. reference temperature 25 °C 77% HHV = _ higher heating value of The values in Table 1-1 for HHV and | BLS, J/kg NHY show thatthe factual energy avail- , Sulfur = weight fraction of elem: able for producing steam in the boiler is e weighs frac Felement early 13% less than indicated by the HHV. Thess fractional sulfur reduction . wiioa ficiency in smelt “Table 1-3 presents assumed operating y conditions for the boiler, which are rea-81 302 °F 226 °F 1562. °F 581 Btu/lb 410 °F 1044 gr/DSCF 230 °F 900 *F 900. psig 1450. Btu/lbm 77 °F | for HHV and al energy avail- in the oiler is dicated by the amed operating which are rea- Chapter 1: General Characteristics of Kraft Black Liquor Recovery Boilers 19 Figure 1-13. Material balance based on 100 kg of black liquor solids. Feedwater, 340 kg Stack gas |_| 7 564 kg Blowdown, 11kg L Dust} recycie 70% solids biack ‘Steam to mill, 314 kg Infitration air, 94.4 kg FD air 405.4 kg hur aris dogo liquor, 142.9 kg |) qi |-+—_; Mao Sean snetio dealing saltcake, 3kg 2.4kg sonable values for a recovery operation, The rate of makeup, recycle, and direct heating are given in Table 1-3. Makeup and recycle were arbitrarily chosen based ‘on experience. The direct heating steam is based on a calculation of the energy required to raise the liquor temperature from the assumed concentrator product temperature to the firing temperature ‘The assumed analysis for the stack partic- ulate is also used for the recycle dust. 1.3.3. Material Balance The information in Tables 1-1 to 1-3 for the fuel analysis and operating condi- tions have been used to make an overall material balance for the recovery boiler shown in Table 1-4. The numbers listed are in kg’s based on 100 kg of dry black liquor solids (BLS) input to the boiler. tank, 47.5 kg This basis is used only for convenience in the size of the numbers presented in the balance, but it does allow the balance numbers to be directly read as wi% of BLS. For each element of the balance, a formula or calculation is shown as well as the values calculated for the example. Each item has a spreadsheet-type refer- ence associated with it, and these refer- ence numbers are used in the formulas. The balance is only for the major flows into and out of the recovery boiler; ie. complete combustion is assumed and minor losses are ignored. The results of the major-flow material balance are shown in Figure 1-13. 1.3.4 Air Infiltration The material balance in Table 1-4 is straightforward, but there are afew20. Kraft Recovery Boilers Table 1-4, Smelt and stoichiometric combustion products for material balance (based ba 100 kg of BLS and 3 kg of saltcake makeup). w x Y Zz 5 tem Calculation kg/100 kg BLS 6 Smelt (ignore Na, from BLS 100°Q17*(78/32/'011 8.78 7 minor losses) from saltcake —-100°QU7*(78/32)"Q14"7 1.47 8 total Zo+Z7 10.25 9 Na,SO, from BLS 100"D117(142/32)"(1-Q17) 178 10 Na’g0 from salteake 100°Q14"(142/32)"(-QU7L7 0.30 u Na.SO, total Z9+Zi0 207 2 NaCl from BLS 400°D12"(58.5/35.5) 0.99 B NaCl from saltcake —--100"Q147(58.5/35.5)"L9 0.01 14 NaCl total Z12Z13 1.00 15 Na,CO, 700°(106/46)" 31.25 [ *(09446/32)'D11 (23/35.5/'D12) 16 K,cO, 100°D10"(138.2/78.2) 2.83 7 Inert 100°D13, 0.10 18 Total smelt ZQ+ZN4Z1A4Z154Z164Z17_—_ 47.50 19 Stoichiometric CO, (44/12)"(100"D64(12/106)"Z15- 114.46 ‘combustion 4{12/138.2°216) 20 products = H,0 100"D7"(18/2} 29.70 21 Oxygen O, for Na,SO, Z117(64/142) 0.93 22 requirement, for Na,CO, Z15*(48/108 14.15 2B CO! required for K,CO, Z16°(48/138.2) 0.98 24 ; required for CO, © 219°(32/44) 83.24 25 Ot required for HG Z20*(16/18) 26.40 26 total O, required Z214Z22+Z23+Z244225 125.71 importane notes regarding infiltration air dnd water vapor in the flue gas. First, the infiltration air to the boiler can be a sub- stantial flow. Modern construction of recovery boilers is generally intended to be gas- tight, but openings in the lower farnace, such as the liquor gun ports and the smelt spouts, do allow air to enter ‘Additional infileration occurs in the back end of the boiler where the waterwall construction stops. Infiltration is driven by the draft, or sub-atmospheric pressure, inside the boiler. [A draft is always used in recovery boil- ers and most other boilers in order to ensuce the safety of operating personnel. ‘With a draft in the furnace, flow is always inward so that smoke, dust, and flames cannot escape through openings. Generally a draft of berween 0,025 and 0.1 kPa (0.1 and 0.4 in. of H,O) is car- Hed in recovery boilers. This value is mea- Sured near the top of the furnace and is Controlled by the operation of the ID fan. The flow of air from the FD fan (or fans) and the volume expansion due to com: bustion are accommodated by the speed of the ID fan. This is called a balanced- rafe situation. The top of the furnace is the balance point. It produces a pressure level in the furnace slightly below atmos- pheric. Starting from the balance point at the top of the furnace, the draft increases | | | | |ralance (based Zz kg/100 kg BLS 8.78 1.47 10.25 ) 1.78 'L7 0.30 2.07 0.99 oot 1.00 31.25 2.83 0.10 1747.50 Z15- 114.46 29.70 0.93 14.15 0.98 83.24 26.40 125.71 st, and flames een 0.025 and of HO) is car- value is mea- furnace and is » of the ID fan, D fan (or fans) n due to com- d by the speed ed a balanced- F the furnace is uces a pressure y below atmos- ce point at the draft increases Chapter 1: General Characteristics of Kraft Black Liquor Recovery Boilers 21 Table 1-5. Air requirement and flue gas flow (based on 100 kg of BLS and 3 kg of saltcake makeup). AC AD AE AF 5 Item Calculation kg/100 kg BLS 6 Air ‘oxygen in BLS and saltcake 100*(08+Q14"L8) 37.04 7 total oxygen required 226 125.71 8 ‘oxygen required from air AF7-AF6 88.67 9 stoichiometric combustion air AF8/0.232 382.19 10 nitrogen in stoichiometric AF9*0.768 293.52 combustion air 1" forced draft (FD) excess air AF9*Q6 22.93 2 total FD air AFS¥AFTT 405.12 13 infiltration air AFo'Q7 34.40 14 total excess air AFITAFI3 57.33 15 Total Air Flow AFO+AFI4 439.52 16 Water steam in stack from 100°(1-Q12/Q12 42.86 vapor water in BL 17 instack direct heating steam 100°Q15/Q12 2.43 gas for liquor 18 humidity in air AFIS*Q10 571 19 sootblowing steam 100°Q35 18.00 20 Total Added Water Vapor AFT6+AFI7+AF18 69.00 21 Flue Gas Total Flue Gas Flow +AFI9 Z19+Z20+AF10+AF14 564.01 +AF20 along the flow path out of the boiler due to the pressure drop resulting from flow through the tube banks in the heat trans- fer section. The draft is also greater in the bottom of the furnace due to the stack effect. The combustion gas inside the fur- nace is less dense than the air surrounding the boiler, so the hydrostatic head due to the height of combustion gas in the fur- nace is less than that for the surrounding air. This difference can be calculated from the simple hydrostatic head equation: AP,,= p,gh (12) where: AP,, = pressure difference between the ottom and top of the furnace, Pa > , = gas density, kg/m? acceleration of gravity, 9.8 m/s? height of the gas column, m «7 The draft in the lower furnace would shen be: Draft= gh Pas Phu) (1-3) For example, the liquor gun ports are approximately 30 m (100 f) below the top of the furnace and, for illustration, the furnace gas can be taken at 1100°C (2012°F) while the surrounding air is taken at 25°C (77°F). The densities are Pg, = 1.01 kg/m? (0.063 Ib/f?) and Pp. °§.303 kg/m’ (0.019 Ib/fe). The draft at22 Kraft Recovery Boilers Table 1-6, Flue gas composition (based on 100 kg of BLS and 3 kg of saltcake make. up). Al 5 Item Calculation 6 mol. wt. of wet flue gas AF21/(Z19/44+AF10/28+ A AK AL 274 +AF14/28.8+(Z20+AF20)/18) 7 totaldry flue gas 8 mol. wt. of dry flue gas ZIS#AFIO+AFI4 AK7/(Z19/44+AF10/ 465.3 kg/100 kg BLS 30.9 28+AF14/28.8) 9 total excess oxygen 10 O, % in wet fue gas 11 0; % in dry flue gas 12 HO % in wet flue gas 13 CO, % in wet flue gas AF14*0.232 the liquor gun ports is then 0.21 kPa (0.84 in. of H,O). This is a very substan- tial driving force for air infiltration The furnace draft also acts on the air ports. The air pressure at the nozzles is measured in the windbox with respect to the local atmospheric pressure. It must be corrected for the additonal deop due t0 the draft in the furnace in order to deter- mine the toral pressure drop across the nozzles. For a pressure at the primary windbox of 0.75 kPa (3 in. of HO), the actual pressure drop across the nozzle would be approximately 0.96 kPa (3.9 in, of HO). 1.3.5 Water Vapor in the Flue Gas Presented in Table 1-5 is a calculation of the total air requirement and the result- ing flue gas flow. Water vapor from a vari- ety of sources contributes to the flue gas flow rate. The tivo largest sources of water vapor are the water in the black liquor (shown in Table 1-5) and the hydrogen in the black liquor solids (shown in Table 1- 4), but sootblowing steam can also be a large source. This will affect the flue gas composition presented later. ‘AK9/32/(AF21/AK6) ‘AK9/32/(AK7/AK8) (220+AF20)/18/(AF21/AK6) Z19/44/(AF21/AK6) 13.3 2.0% 2.8% 26.7% 12.7% kg/100 kg BLS 1.3.6 Flue Gas Composition ‘The composition of the flue gas is pre- sented in Table 1-6, The flue gas O, reflects the amount of excess air used in combustion. All combustion systems use some excess air in order to overcome the limitation of incomplete mixing and achieve complete combustion, The two basic methods for measuring O,96, dry. basis and wet-basis, differ ‘in their reported value. In the dry-basis measure- ment, a sample of the flue gas is with- drawn from the boiler. This sample is cooled and most of the water vapor is removed so that the 0.9% in the dry fluc gas is proportionately higher than in the actual wet flue gas. The wet-basis mea- surement of ©,% is usually an in-situ measurement of the actual ©,% in the wet flue gas. The wecbasis is the more common measurement today for recovery boilers. Both values are listed in Table 1- 6, and 2 substantial difference can be seen beoween the two. It is, therefore, impor- tant to know the basis on which O, values are reported when making comparisons of boiler operation. The general relationship between excess air and measured O,% is easy 10 detive from the stoichiometric relation:of saltcake make- AL 3 kg/100 kg BLS kg/100 kg BLS % ‘position the flue gas is pre- The flue gas 0,96 excess air used in aston systems use 'T to overcome the ilete_mixing and bustion. The two suring O,%, dry. sifer‘in ches iry-basis measure- lue gas is with. t. This sample is le water vapor 9% in the dry flue ‘igher than in the e wet-basis mea- sually an in-situ al 0.% in the basis is the more today for recovery listed in Table T- rence can be seen therefore, impor- which ©, values ing, comparisons onship between 0,% is easy to pméttic relation Chapter 1: General Characteristics of Kraft Black Liquor Recovery Boilers 23 Figure 1-14, Excess air versus oxygen concentration in flue gas. 6 40 as + 30 28 20 Excess Air, % 1 10 Flange for wot basis measurements 25 3 98 4 48 5 Og in Fiue Gas, % ships. Presented in Figure 1-14 are curves of excess air versus O,% for both a wet- basis and a dry-basis. measurement. Expressions for each are presented in Equations (1-4) and (1-5). It is not ob ous from the equation, but the dry-basis measurement is very insensitive to liquor composition. In fact, the same dry-basis ‘curve can be used for fossil fuels as well as Dry Basis: Excess Air Fraction nee | 376+ T-476(0,%ab) Wet Basis: Excess Alr Fraction = O28 _| 76,4 - 46 1-476 (0,%00)| °°" Ca nea for black liquor. The dry-basis curve is shown as a single universal ine in 1-14. The wet-basis measurement is sen- sitive to fuel hydrogen content as well as added water such as sootblowing steam. It is shown as a band of values in Figure 1- 14. The band is sufficiently narrow so that using the average value is adequate tunder most circumstances in a kraft mill Ne_K Safar C1 Ht added water 2 Ta 3° 92156" 1a 3224 Kraft Recovery Boilers where: 0,%db O,%wb added wacer CH, Na, Sulfur ‘oxygen concentration in flue gas measured on a dry basis, % vol (expressed as a fraction) ‘oxygen concentration in flue gas measured on a wet basis, Yovol (expressed as a fraction) weight fraction of water and steam added to the boiler including water in BL, humidity in air, direct heating steam, and soot blowing steam, kg/kg BLS weight fraction of element in BLS Table 1-7. Conversion efficiencies and losses (based on 100 kg of BLS and 3 kg of saltcake makeup). AO AP AQ AR 5 Item Calculation g/100 kg BLS 6 Carbon and H,, in flue gas AK7*Q25"1E6"2/AKB 0.006 7 Hydrogen Conversion % hydrogen converted Efficiencies to HO (220°2/18-AR6)/(Z20"2/18) 99.8% 8 CO in fue gas Q24*1E-6°28°AK7/AKB 0.08 9 carbon in smelt Zis'Qis 0.48 10 total carbon available Z19"12/44 31.22 for combustion " ‘% carbon converted —_(1-AR9/AR10. 98.36% to CO, (12/28)*AR8/AR10) 2 % carbon in smelt ARS/ARTO 1.52% 13 % carbon in CO (12/28)*AR8/AR10 012% 14 Sulfurloss total sulfur to boiler 100*(011+Q14°L7) 467 15 fromRB ——sulfurinstackSO, -_Q23*1E6°AK7*(32/AK8) 0.03618 16 sulfur in stack TRS Q22*1E6*AK7*(32/AK8)__ 0.007 17 stack particulate flow Q26"1E3°AK7/(0.0422°AK8) 0.036 18 sulfur in stack particles ARI7"Q33 0.007 9 2% sul loss (ARIS*ARTG+ARTBY/ARTA 1.08% 20 sulfur in dust recycle 100*D9"Q16"Q33/Q32— 1.23 21 total sulfur in flue gas. ARZO+ARTS+AR16 1:28 2 % sulfur in flue gas ARI6/AR21 057% not oxidized 23. Sodium Loss total Na to boiler 100*(09+Q14*L6) 2067 24 fromRB Nain stack particulate ARI7*Q32 1.11% 25 % Na loss AR24/AR23 0.05%a dry basis, % vol a wet basis, %6vol e boiler includin, am, and soot 3 and 3 kg of kg/100 kg BLS 0.006 18) 99.8% 0.08 0.48 31.22 98.36% 1.52% 0.12% 4.67 } 0.03618 ) 0007 AK8) 0.036 0.007 14 1.08% 1.23 1.28 057% 20.67 1.11% 0.05% Chapter 1: General Characteristics of Kraft Black Liquor Recovery Boilers 25 1.3.7. Carbon, Hydrogen, and Sulfur Conversion Efficiencies Table 1-7 shows the carbon and hydrogen conversion efficiencies. The surpose of the combustion process is to Foner all hydrogen to water vapor and all carbon to either CO, or carbonate. H, and CO in the flue gas and carbon in the smelt account for the major inefficiencies in the conversion. Extremely small quan- tities of hydrocarbons and carbon also escape with the flue gas. The H, content of the flue gas is rarely measured, but ‘measurements elsewhere have repeatedly shown that the water/gas shife equilibri- tum always results in approximately equal CO and H, concentration in flue gas from combustion. Water - gas shift equilibrium: CO, +H, CO+H,O (1-6) Even at the level of H, assumed here, the hydrogen conversion efficiency is very high, 99.89%. At complete equilibrium, the flue gas concentration of CO and other products of incomplete combustion would be less than 1 ppmv. CO cannot coesst with O, in equilibrium above this level at ordinary temperatures. Moreover, the reaction of O, with CO ‘and other incomplete com- bustion products is very rapid. Ar furnace temperatures above 900°C (1650°F), these reactions are 99.99% complete in less than 100 milliseconds. CO should not be found in the flue gas unless che CO and O, are not fully mixed during the combustion process. Similar observa tions in many other combustion situa- tions have led to the combustion engi- neer’s rule of thumb that mixed is burned. Each of the other gas-phase products of incomplete combustion, H, and total reduced sulfur (TRS), would be reduced to very low levels in the flue gas leaving the boiler if incomplete mixing could be eliminated. CO and TRS excur- sions in the furnace exit gas tend to occur simultaneously in normal operation because they both resule from poor mix- ing. This is why control of CO normally also controls TRS. ‘The general level of TRS is nearly two orders of magnitude below the level of CO. This reflects differences both in the quantity of input and reactivity of the gases. Approximately ten times as much carbon as sulfur enters the boiler, so dif- ferences of this order of magnitude would be reasonable for these minor products of incomplete combustion. However, the sulfur compounds are also more reactive than CO, leading co a further difference in their ultimate concentration ratio. The level of TRS generated in the combustion zone will depend on the liquor sulfidity and its oxidation state, bue the ultimate level in the flue gas will depend strongly on the air mixing in the furnace. As shown in Table 1-7, the carbon conversion efficiency is not as high as the hydrogen conversion efficiency. This is largely due to the unburned carbon in the smelt. For the gas phase, the conversion efficiency for carbon is approximately 99.88%. Both hydrogen and earbon con. version efficiencies are quite high. For boilers, even with substan higher CO levels, the loss in energy is low. Ignoring the CO and H, in the material and enets gy balances does not affect the results sig- nificantly and simplifies the calculation substantially, Most of the sulfur entering the recov- ery boiler leaves with the smelt. However, some sulfur is lost from the stack as SO,, TRS gases, and as Na,SO,. The TRS gases are taken ‘here as HLS for convenience, though in practice they usually contain mercaptans. As seen in Table 1-7, the major loss is from SO, despite the rather modest value of 75 ppmv used in this example. The total sulfur loss from the stack at this SO, level is only 1.08%, indi- cating that the Major sulfur (and sodium)26 Kraft Recovery Boilers ‘Table 1-8. Energy balance for a kraft black wor recovery boiler. AV AW AX AY AZ 5 tem Calculation Kjy/kg BLS % 6 Heat heating value of BL solids D15 93.76% 7 Input sensible heat in BL (1/Q12)°2.65°(Q13-25) 211% 8 sensible heat in air (AF15/100)"1.006"(Q9-25) 0.06% 9 heat to preheat air (AFI2/100)"1.006" (Q11-Q9)501 10 heat in feedwater ‘AF19/100"4.19"(Q36-25) 64 0.43% for sootblowing steam u heat in feedwater Q34"4.19°(Q36-25) 39 0.26% for blowdown 2 Total Heat Input AYO+AY7+AYB*AY9* 14878 100% +AYIOFAYIT 13 Heat sensible heat in (AK7/100)*1.02(Q21-25) 878 5.90% dry flue gas 14 Output heat loss from hydrogen (Z20/100)"(2770+ 629 557% in BLS +1.98"(Q21-200)) 15 heat loss from water in BL (1/Q12-1)*(2770* 1,196 8.04% +1.98"(Q21-200)) 16 sensible heat in smelt (218/100)*Q20 641 431% 7 heat to form sulfide (za/100)"12900 1,322 8.89% 18 heat loss from sootblowing (AF19/100)"(2770+ 502 3.38% steam +1.98"(Q21-200)) 19 heat loss from blowdown Q34*1150 127 0.85% 20 radiation loss typically 0.3 % of heat input 45 030% an unaccounted losses typically 2.0 % of heat input 298 2,00% 2 Total of Losses _AYISEAYLAFAYISHAYI6+ 5,837 39.23% “AYI7+AY18#AY19#AY204 +AY21 23 heat to steam AYIZAY22 9041 60.77% 24 Total Heat Output AY22+AY23 14,878 100% Joss from the mill occurs outside the recovery department. However, for mills which operate with more than a few hun- dred ppm of SO, in the stack, sulfur loss from this source would be substantial. ‘A great deal more of the sulfur recy- cles within the recovery boiler system due to fume generation and liquor droplet carryover. The majority of this material is Na,sOy, and ie is recycled through the economizer hoppers and the electrostatic precipitator to the mix tank. Sulfur con- tained in the fume, SO, and TRS repre- sents nearly 26% of the sulfur entering the boiler, All of this material originates {s reduced sulfur compounds in the lower famnace. Most of it reacts with oxygen t0 form SO, and $O,, which further reacts with volatilized sodium to form Na,SO, The TRS in the stack is the sulfur whicl was not oxidized in the furnace. TRS tep~ Tesents only 0.55% of the sulfur that flies in the farnace. As with carbon and bydro- gen, the sulfur combustion efficiency isAY AZ Kj/kg BLS % 13,950 93.76% 314 2.11% 9 0.06% 3.37% 64 0.43% 39 0.26% 14878 100% 878 5.90% 829 5.57% 1196 8.04% 641 431% 1322 8.89% 502 3.38% 127 0.85% 45 0.30% 298 2.00% 5,837 39.23% 9,041 60.77% 14,878 100% ), and TRS repre- he sulfur entering material originates ounds in the lower cts with oxygen to hich urcher reacts n to form Na,SO, is the sulfur which furnace. TRS rep- the sulfur thae flies carbon and hydro- istion efficiency is Chapter 1: General Characteristics of Kraft Black Liquor Recovery Boilers 27, Table 1-9. Steam flows from material and energy balances. BC BD BE BF 6 steam to mill AY23/(Q39-104.8-4.197(Q36-25))-3.11_ke/kg BLS 7 feedwater to boiler BE6+Q34+Q35, 3.40 ke/kg BLS 8 %of feedwater in BE6/BE7 91.5% mill steam . 9 % of feedwater Q35/BE7 5.3% in sootblowing 10. % of feedwater Q34/BE7 3.2% in blowdown quite high at 99.45%. The inefficiency is again due to incomplete air mixing. 1.3.8 Energy Balance Once the material balance is estab- lished, ic is a straightforward matter to complete the energy balance. The energy balance for the example case along with the calculation procedure is shown in Table 1-8. Note that the values are reported in kJ/kg of BLS, not per 100 kg of BLS, and this heat balance is only for the major flows. The final cerm, heat to steam, is obtained by difference, auto- matically closing the balance. The tech- nique shown is universally used for boil- ers and other combustion devices to cal- culate energy efficiency because it does not depend on the measurement of flows. Ieis called the Heat Loss method and is the basis of the TAPPI Short Form method, The basis for the heat input is the higher heating value, HHV, which accounts for nearly 94% of the energy input. As mentioned above, the loss in energy due to hydrogen in the BLS, water in the black liquor, and heat of reduction to form NaS ate all taken into account directly as loss terms in the output. They are the three major heat loss terms, with sensible heat in the dry flue gas, sensible heat in the smelt, and sootblowing steam also being important. The net energy available er steam production is taken as the difference berween the input and the losses and is 60.8% for this example. Lower excess ais, lower sulfidity, lower economizer exit temperature, and higher liquor percent solids would all increase this value. Higher liquor percent solids would have the largest impact on boiler efficiency. There would be no measurable improvement in this value from reduc- tion of minor losses such as CO and H. Carbon in the smelt, on the other hand, is a minor loss that would have more impact on the efficiency. It represents 1.54% of the combustible carbon enter- ing the boiler and about 1% of the ener- gy. which is enough to merit optimiza- tion, There aze also compelling environ- mental and operational reasons to reduce these minor losses Table 1-9 shows a calculation for the quanti of team produced per ig of BLS fired. With the assumed blowdown and sootblowing usage, the energy for steam econ cgi ee gi ee steam per kg of BLS. The required feed- water flow and che breakdown of where it goss is also shown in Table 1-9. The black liquor dry solids is the vari- able with the largest impact on the boiler28 Kraft Recovery Boilers efficiency. Table 1-10 shows the efficien- cy for several levels of BL dry solids when all other parameters are as specified in Table 1-3, 1.4 FURNACE COMBUSTION PROCESSES 1.4.1 General Furnace Processes The overall process of black liquor combustion requires the addition of heat and air (oxygen) to the black liquor droplets. The heat is required to dry and pyrolyze the liquor while air is required for oxidation of the organic matetial. The overall process is very similar to that for other fuels burned in boilers. However, two very unique aspects of recovery boil: cers are: 1) the air and fuel are introduced entirely separately and 2) the fuel is not finely divided. Routine combustion of fossil fuels sees the use of swirl burners or burner guns in which substantially all the air is introduced in the immediate vicin- ity of the fuel. This promotes rapid and complete mixing. In addition, liquid and solid fossil fuels are always very finely divided to increase the surface area avail- able for heat and mass transfer. This shortens both ignition and final burnout times. In strong contrast co this usual sit- uation, the fuel and air ina recovery boil er ate introduced separately, and droplets an order of magnitude larger than typical fossil fuel sizes are used. ‘The reasons for this involve the very high inorganic con- tent of the liquor, the need to avoid entrainment, and the need to build a bed on the furnace floor to aid sulfur reduc- tion and smelt removal. 1.4.2. Flame Temperature Some insight into black liquor as a fuel and its impact on furnace perfor- Table 1-10. Boiler efficiency for several levels of BL dry solids, BL dry solids Boiler efficiency 60% 56.5% 5% 58.8% % 60.8% 75% 62.5% 80% 64.0% 85% 65.4% mance can be obtained from a calculation of the flame temperature. The actual tem- peratures in a recovery furnace vary from point to point and with time, even under steady state conditions. The temperature field is a complex result of gas flow pat- terns, combustion patterns, and the resulting incricate heat radiation fields. However, a global energy and heat trans: fer calculation can reveal general levels of temperature and the wrends in these levels with changes in many input variables This approach fils at revealing details or complex interactions between variables, but does reveal some practical observa- tions about the relative magnitude of the impacts of variables like black liquor dry solids, firing rate, and furnace size, The global calculation assumes that all the chemical energy in the fuel is used to: 1) raise the temperature of the combustion gases, 2) raise the temperature of the smelt and, 3) transfer heat by radiation to the adjacent waterwalls. The net heating value NHV characterizes the amount of energy actually available in the fuel, so an energy balance would yield the following ft |Chapter 1: General Characteristics of Kraft Black Liquor Recovery Boilers, 29 ncy for several Heat to evaporate water {eter enery released fom fl see et in combustion products and ds oiler efficiency |+ sensible energy in fuel and air +-sensible heat in smelt ae radiation heat transfer tothe waterwalls 56.5% 588% Ha Jn equation form: : aca | Gius(NHV)F, + (Gu + Gy + Gc + Gan) os (Top —Prg)}* Gs Ta ~Tr) = 65.4% = GAM, +(G, +Gaa)OD, [Te Tay) * Goes ama +(€,4WLe +1006 }W om a calculation with “The actual tem- inace vary from LFA ime, even under Che temperature of gas flow pat- terns, and the radiation fields. -and heat trans- eneral levels of in these levels nput variables. vealing details or tween variables, ‘actical observa~ Cp, = he f ED air = 1,010 J/kg/*C Cp, \eat capacity of air = 1,010 J/kg/' Bee eee Chy = heat capacity of black liquor, Jkg/®C : heat capacity of combustion products, J/kg/*C + leje (t+ 2) (LFA—1 ep (1-8) amnace size. The nes that all the ad is used to: 1) the combustion perature of the sensible heat in smelt, J/kg enthalpy of vaporization of water, kg gas emissivity, unitless nen Cie = lower furnace excess air required for complete com bustion, unitless nie armen a fraction of NHV released in lower furnace, unitless nthe fuel, so an G, = flow rate of FD air, kg/s \d the following: G,, flow rate of black liquor solids, kg/s G,,, = flow tate of precipitator dust, kg/s ] Gyuo = flow rate of water vapor in the combustion products, kg/s G flow rate of gaseous combustion products, kg/s G. = flow rate of saltcake makeup, kg/s Gu, = flow rate of smelt, kg/s G_” = flow rate of water contained in black liquor, kg/s L, = lower furnace height, m30 Kraft Recovery Boilers LFA fraction of stoichiometric air in lower furnace Stefan-Boltemann constant, 5.67x10® W/m’/K4 weight fraction of dry solids in black liquor preheat temperature of FD air, °K flame temperature, °K reference temperature = 298°K T, cc = s T, Ty black liquor temperature, T at 2 furnace wall temperature, °K w farnace wall horizontal dimension, m Note that the value of NHV must be expressed in units of J/kg rather than ‘jg in Equation (1-7). Also, the black liquor flow rate is for the virgin liquor, not the as- fired liquor, and the dust is all the carryover and fume material that passes our of the furnace. ‘The parameter F, is the fraction of the NHV ‘eleased inthe lower furnace When the fraction of air delivered to the lower furnace is less than the chemically correct (stoichiometric) amount, only a portion ofthe liquor cn buen and release eat. When the fraction of air in the lower furnace is well above the stoichio- metric amount, then all the chemical energy in the black liquor fuel is released, Between these two limits the fraction “of the NHV released is dependent on the degree of mixing in the lower furnace. Poorer mixing results in less of the liquor being burned. This pattern is shown in Figure 1-15 for perfect mixing and for poorer mix requiring 40% excess air in the lower furnace for complete combus- tion of the fuel. There is no established method for characterizing the degree of mixing in the lower furnace. The curved portion of the poor mixing curve in Figure 1-15 is nec- essarily only a rough approximation, and the equation for F, is only a convenient, smooth curve that approximates the impact of poor mixing. However, the equation for Fh and Figure 1-15 do reHlect physically realistic levels of mixing completeness. Under ordinary circum stances, about 120% of stoichiometric air (i.e. 20% excess ait) is required to attain nearly complete combustion in the fur- nace of a recovery boiler. It is reasonable that between 120% and 140% would be required to attain complete combustion in the lower portion of the furnace, The mixing model above in Equation (1-8) uses the parameter e,,, the excess air to achieve complete combustion in the lower furnace, as the measure of mixing. The perfect mixing curve in Figure 1-15 is for e,. = 0, ie. no excess air would be required for complete combustion in the lower furnace. The poorer mixing curve is fore, = 40%, ie. excess air of 40% for complete combustion, which is probably realistic for poorer mixing in many recov- ery boilers. The gaseous combustion products are the sum of the fuel (BLS), the water that accompanies the fuel, and the combus- tion air, less the mass of material leaving as smelt, The ratios G/G,, and G./G,, can be obtained directly from the miteri= al balance in Table 1-5 or from the expressions below: (LFAYAFS)igute 1-15 do levels of mixing dinary circum: oichiometric air quired to attain Hon in the fur- It is reasonable 140% would be ete combustion he furnace. The Equation (1-8) he excess air to sustion in the isure of mixing. e in Figure 1-15 ss air would be nbustion in the mixing curve s air of 40% for on products are y a water that id the combus- material leaving 3,, and G/Gy. rom the materi- 5 or from the FS) (1-9) Chapter 1: General Characteristics of Kraft Black Liquor Recovery Boilers 31 Figure 1-15. Heat release as a function of the lower furnace air fraction showing the effect of poor mixing. 100% 90% 80% 70% 60% 40% 30% 20% Fraction of NHV Released in Lower Furnace 8 g 10% Oe 20 40) co Perfect mixing Imperfect mixing requiring 40% excess air in lower furnace for complete ‘combustion ________| 80 100120 140160, Lower Fumace Fraction of Theoretical Air, % where: AFS = stoichiometric air-to-fuel ratio, unitless IS, Gre, Ga Game + Se 4 Se Smt Gry Gone Gone (1-10) ‘The heat capacity Cp, is the average value for the temperature’ range between 298°K (25°C or 77°F) and T,. The pri- mary combustion products, ‘CO,, N,, and O, all have very similar values Of Cp, buc water vapor does not, Water vapor has a Cp approximately double hat of the others so a good approximate value for Cp, in the flame temperature calcula- tion would be: eee cee Breer lta: any where: Gyo = flow of water vapor in the combustion product, ke/s Cpyq = average heat capacity of N, up “to 1300°C (2372°F) = 1,150 WhgleC ‘The value of heat capacity is an aver- age value for the temperature range of interest in the flame calculations.32 Kraft Recovery Boilers Table 1-11, Parameters for the flame temperature calculation. Constants AFS 3.82 HHV 13,950,000 Jykg BLS NHV 12,093,000 J/kg BLS Hydrogen 0.033 ka/kg BLS GsmelVGi 0.475 kaykg BLS Gse/Gf 0.03, g/kg BLS GdusyGf 0.06 g/kg BLS Cpa 1,010 kerr Cpbl 2,820 kerr ©, gas, 0.45 emissivity H 8 m Twall 800 °K Tref 298 °K Ahsmelt 1,350,000 /kg Ahwater 2,440,000 /kg Variables Dry solids 0.7 keke BL fraction Ta 400 °K LEA, fraction 1.0 theoretical elice 03 Gt 16 ke/s L 9 m Calcul Ga 61.12 ke/s Gw 6.86 ke/s Gse 0.48 kes Gust 0.96 kis Gsmelt 7.60 ke/s Gp 76.86 kg/s ee 11.61 els Cop 1324 kel" HHRR 2756 kW/m?2 Fh 0.93 Flame temperature 1 1473 °K i 1,200 Ke T 2192 F Gyao/Gp can be represented by the prod- uct (Gao/G)G, /G,,) with Gio _ 18) 1-8 + G, 2S (1-12) The energy balance for the lower fur- nace presented in Equation (1-7) has been, solved for the flame temperature, T,, for a range of conditions. The flame temperature calculated in this way is only a global indicator of temperature levels in the furnace. The actual gas temperature ‘would vary throughout the lower furnace and would be different for the char bed. However, the calculated flame tempera. ture will indicate the correct levels and tends for temperature in this region of the furnace. The calculations have been done for the black liquor described in Tables 1-1 through 1-3. Table 1-11 lists values for the various parameters in Equation (1-7) along with values for liquor dry solids, air preheat temperature, lower furnace fraction of stoichiometric air, liquor firing rate, excess air for com- plete combustion in the lower furnace (mixing parameter), and furnace size used as the mid-range values,Chapter 1: General Characteristics of Kraft Black Liquor Recovery Boilers 33 Figure 1-16, Impact of liquor dry solids on the calculated flame temperature, 1900 kg/s 2300 tes 1250 els ke/s e kes > 200 2200 * kg/s g a 5 kg/s a & sfkg/"C 2 1150 2100 B kW/m" é e e e 2 "| 2000 “K 1050 fc 1900 °F 1000 60% 65% «= 70% «= 75% «80% BM Black Liquor Dry Solids, % Figure 1-17. Impact of air preheat on the calculated flame temperature. ‘Ar Preheat Temperature, °F 225 250275 900825 1300 ++ | 2300 1250 ior the char bed. flame tempera- ° ¥ orrect levels and %5 1200 zz00 n this region of 2 2 tions have been 5 2 cor described in & 1150 72100 2 Table 1-11 lists 5 | & parameters in e £ with values for & 1100 2000 & eat temperature, a f stoichiometric ‘ess air for com- 1080 | 1800 lower furnace 100 128 Air Preheat Temperature, °C furnace size used $000 |—___+» ___+—_ 160 175