Chap 28 PDF

The Babcock & Wilcox Company
Chapter 28
Chemical and Heat Recovery
in the Paper Industry
In the United States (U.S.), the forest products in- ing its name from the use of sodium sulfate (Na2SO4)
dustry is the third largest industrial consumer of en- as the makeup chemical. The paper produced from this
ergy, accounting for more than 11% of the total U.S. process was originally so strong in comparison with
manufacturing energy expenditures. In 2002, 57% of alternative processes that it was given the name kraft,
the pulp and paper industry relied on cogeneration which is the Swedish and German translation for
for their electric power requirements. strong. Kraft is an alkaline pulping process, as is the
Approximately one-half of the steam and power con- soda process which derives its name from the use of
sumed by this industry is generated from fuels that sodium carbonate, Na2CO3 (soda ash), as the makeup
are byproducts of the pulping process. The main chemical. The soda process has limited use in the U.S.
source of self-generated fuel is the spent pulping li- and is more prominent in countries pulping nonwood
quor, followed by wood and bark. The energy required fiber. Recovery of chemicals and the production of
to produce pulp and paper products has been signifi- steam from waste liquor are well established in the
cantly reduced. Process improvements have allowed U.S. kraft and soda processes. The soda process accounts
pulp and paper manufacturers to reduce energy con- for less than 1% of alkaline pulp production and its
sumption to 2.66 × 1012 Btu (2806.5 × 1012 J), a signifi- importance is now largely historic.
cant reduction.
Pulp and paper mill electric power requirements
have increased disproportionately to process steam Kraft pulping and recovery process
requirements. This factor, coupled with steadily ris-
ing fuel costs, has led to the greater cycle efficiencies Kraft process
afforded by higher steam pressures and temperatures The kraft process flow diagram (Fig. 2) shows the
in paper mill boilers. The increased value of steam has typical relationship of the recovery boiler to the over-
produced a demand for more reliable and efficient heat all pulp and paper mill.1 The kraft process starts with
and chemical recovery boilers. feeding wood chips, or alternatively a nonwood fi-
The heat value of the spent pulping liquor solids is brous material, to the digester. Chips are cooked un-
a reliable fuel source for producing steam for power der pressure in a steam heated aqueous solution of
generation and process use. A large portion of the
steam required for the pulp mills is produced in highly All Other USA
31%
specialized heat and chemical recovery boilers. The Countries
30%
balance of the steam demand is supplied by boilers
designed to burn coal, oil, natural gas and biomass.
Major pulping processes

The U.S. and Canada have the highest combined
consumption of paper and paperboard in the world
(Fig. 1), consuming 105.6 million tons each year. With
a base of more than 800 pulp, paper and paperboard
mills, the U.S. and Canada are also the leader in the
production of paper and paperboard. North America Canada
2%
accounts for 32% of the total world output; pulp pro- Italy
duction is nearly 43%. 3%
Peoples Republic
Total pulp production in the U.S. is divided among France
3%
of China
11%
the following principal processes: 85% chemical, United Kingdom 4%
groundwood and thermomechanical; 6% semi-chemi- Germany Japan
cal; and 9% mechanical pulping. The dominant North 6% 10%
America pulping process is the sulfate process, deriv- Fig. 1 World paper and board consumption by country, 2000.
Steam 41 / Chemical and Heat Recovery in the Paper Industry 28-1

Fig. 2 Kraft process diagram.
sodium hydroxide (NaOH) and sodium sulfide (Na2S)

known as white liquor or cooking liquor. Cooking can
take place in continuous or batch digesters.
After cooking, pulp is separated from the residual
liquor in a process known as brown stock washing. The
most common method features a countercurrent se-
ries of vacuum drum washers which displace the li-
quor with minimum dilution. Following washing, the
pulp is screened and cleaned to remove knots and
shives and to produce fiber for use in the final pulp
and paper products.
The black liquor rinsed from the pulp in the wash-
ers is an aqueous solution containing wood lignins,
organic material, and inorganic compounds oxidized
in the cooking process. Typically, the combined organic
and inorganic mixture is present at a 13 to 17% con-
centration of solids in weak black liquor. The kraft
cycle processes this black liquor through a series of op-
erations, including evaporation, combustion of organic
materials, reduction of the spent inorganic compounds,
and reconstitution of the white liquor. The physical
and chemical changes in the unit operations are
shown in Fig. 3.2
The unique recovery boiler furnace was developed
for combusting the black liquor organic material while
reducing the oxidized inorganic material in a pile, or
bed, supported by the furnace floor. The molten inor-
ganic chemicals or smelt in the bed are discharged to
a tank and dissolved to form green liquor. Green li-
quor active chemicals are Na2CO3 and Na2S.
Green liquor contains unburned carbon and inor-
ganic impurities from the smelt, mostly calcium and
iron compounds, and this insoluble material, or dregs,
must be removed through clarification. This operation
is basically settling of sediment and decantation of Fig. 3 Kraft process cycle.
28-2 Steam 41 / Chemical and Heat Recovery in the Paper Industry

clear green liquor that can be pumped to the slaker. ids contained in the recovered liquor. Because the
The dregs are pumped out of the clarifier as a concen- proper measure of recovery boiler capacity is the heat
trated slurry. Normal operation is to water wash the input to the furnace, The Babcock & Wilcox Company
dregs before landfill disposal. The water wash liquid (B&W) has established a 24 hour heat input unit of
containing the recovered sodium chemical is known 19,800,000 Btu (20,890 MJ). This unit, known as a
as weak wash. The sodium chemicals are recovered by B&W-Btu ton, corresponds to the heat input from
using the weak wash to dissolve the smelt in the dis- 3000 lb (1361 kg) of solids (approximately equivalent
solving tank. to one ton of pulp produced) having a heating value
Clarified green liquor and lime (CaO) are continu- of 6600 Btu/lb (15,352 kJ/kg) of solids. These were
ously fed to a slaker where high temperature and averages for the typical black liquor solids generated
agitation promote rapid slaking of the CaO into cal- from a ton of kraft pulp production when this unit was
cium hydroxide (Ca(OH)2). The liquor from the slaker originally defined. The black liquor solids produced
flows to a series of agitated tanks that allow the rela- from modern operations generally are characterized
tively slow causticizing reaction to be carried to by considerable variation in the quantity of the solids
completion. The function of the causticizing plant is per ton of pulp product and somewhat lower heating
to convert sodium carbonate into active NaOH. The values. For this reason, a more common rating term
calcium carbonate (CaCO3) formed in the conversion applied to current recovery boilers is the amount of
reaction precipitates in the causticizing operation to dry solids processed over a given period of time (hour
form a suspended lime mud. or day). The recovery boiler is a heat input machine,
The causticizing product must be clarified to remove and as such, The B&W-Btu rating recognizes the true
the CaCO3 precipitate and produce a clear white liquor indication of the unit’s design capacity to process that
for cooking. This clarification is carried out by either energy input.
settling and decanting, in a manner similar to green The nominal size of a B&W kraft recovery boiler can
liquor clarification, or by using pressure filters. In be determined by application of a simple formula as
pressure filtration, the white liquor is filtered through follows:
a medium to provide a separation of clear white liquor
from the lime mud. The lime mud is then washed to A × B × C
Nominal size = , B&W-Btu tons (1)
remove sodium chemicals that can lead to increased 19, 800, 000
kiln emissions and clinkering, and further filtered to
obtain the desired consistency for feed to the kiln. where
The lime kiln calcines the washed lime mud feed into A = dry solids recovered, lb/t of pulp
reburned lime. Calcination is the chemical breakdown B = pulp output of mill, t/24 h
with heat of the CaCO3 into active lime and carbon C = heating value of dry solids, Btu/lb
dioxide (CO2). The calcined lime is then slaked as pre-
viously described. and 19,800,000 is the product of 3000 lb/t and 6600
The reactions occurring in the solids cycle operations Btu/lb.
are as follows: Today’s recovery furnace is conservatively designed
for a heat release rate (heat input rate divided by
Slaking: CaO + water = Ca(OH)2 + heat
furnace plan area) of approximately 0.90 × 106 Btu/h
Causticizing: Ca(OH)2 + Na2CO3 = CaCO3 + 2NaOH ft2 (2.84 MW/m2 ). This heat release has increased over
time, but was always kept below 1.0 × 106 Btu/h ft2
Calcination: CaCO3 + heat = CaO + CO2
(3.15 MW/m2 ). Although new recovery boiler furnaces
The combination of these process steps is referred to are sized for a low heat release rate, there are many
as recausticization. recovery boilers that have experienced successful ca-
In parallel with the reduction of sulfur compounds pacity increases at much higher heat release rates.
to form smelt, energy is released in the recovery fur- Mills historically have increased pulp production mak-
nace as the black liquor organic compounds are com- ing the recovery boiler a limiting factor at the mill. In
busted. This combustion energy is used in the process order to maintain increased pulp production, the re-
recovery boiler to produce steam from feedwater. The covery boiler has been called upon to process an ever
steam can be introduced to a turbine generator to increasing amount of black liquor solids. Today it is
supply a large portion of the energy demand of the common for a recovery boiler to successfully process
pulp and paper mill. Steam extracted from the turbine solids that result in heat release rates up to 1.25 × 106
at low pressure is used for process requirements such Btu/h ft 2 (3.94 MW/m 2 ). This has been achieved
as cooking wood chips, evaporation, recovery furnace through improvements to the combustion air and li-
air heating, and drying the pulp or paper products. quor delivery systems, sootblower systems, reduction
of chlorine in the as-fired liquor, and changes to con-
Rated capacity of a recovery unit vection pass arrangements.
The capacity of a pulp mill is based on the daily tons There are several criteria commonly used to evalu-
of pulp produced. The primary objectives of a recov- ate the potential success of capacity increases for re-
ery boiler are to reclaim chemicals for reuse and to covery boilers. In addition to the heat release rate, the
generate steam by burning the black liquor residue. furnace exit gas temperature, superheater exit gas
Accordingly, the capacity of the recovery boiler should temperature, flue gas velocity, and furnace volume
be based on its ability to burn or process the dry sol- are important criteria. Depending on the extent of the

capacity increase, most of these criteria can be met with to the feedwater in generating steam and can be ex-
changes to the original design. For example, flue gas pressed as:
temperatures can be reduced with furnace screen and
superheater changes. Furnace volume has been modi- Output = ( H s − H fw ) m
, Btu/h ( J / s ) (2)
fied by expanding the furnace forward, relocating the
furnace front wall forward and making the side walls where
wider thus providing a greater furnace volume for
H s = enthalpy of steam leaving superheater, Btu/
higher rates of liquor solids.
lb (J/kg)
The criteria B&W uses to predict recovery boiler
Hfw = enthalpy of entering feedwater, Btu/lb (J/kg)
performance is based on operating experience. Some
of this has changed over time as equipment improve- m = steam or water flow rate, lb/h (kg/s)
ments have affected operation. Boiler water is frequently withdrawn from the
steam drum as blowdown to maintain steam purity.
Process flows through the recovery boiler Steam may also be withdrawn prior to the final su-
The kraft process recovery boiler is similar in many perheater stage for use in sootblowing. In these in-
respects to a conventional fossil fuel-fired boiler. The stances, the output expression must be corrected to
concentrated black liquor fuel is introduced into the account for the energy leaving the boiler prior to the
furnace along with combustion air. Inside the furnace, superheater outlet.
the residual water is evaporated and the organic
material is combusted. The inorganic portion of the
black liquor solids is recovered as molten smelt. Most
of the sulfur is in the reduced form of Na2S and most
of the remaining sodium is Na2CO3. The requirement
to recover sulfur in a reduced state is the most unique
aspect of recovery boiler design. Fig. 4 illustrates a typi-
cal modern recovery boiler.
Combustion air is introduced into the furnace at
staged elevations: primary, secondary, tertiary, and at
times, quaternary. One-fourth to one-half of the air
enters at the primary level near the furnace floor. The
balance is staged at the secondary, tertiary and qua-
ternary levels. Heavy black liquor (solids greater than
60%) is fed to the furnace through multiple burners
between the secondary and tertiary air levels.
The gases generated by the black liquor combus-
tion rise out of the furnace and flow across convection
heat transfer surface. Superheater surface is ar-
ranged at the entrance to the convection pass, followed
by steam generating surface and finally the econo-
mizer. In designs featuring direct contact evaporators,
the flue gas may flow from the boiler bank to the
evaporator with no economizer surface provided, or a
relatively small economizer may be required.
Feedwater enters the recovery boiler at the bottom
of the first pass economizer. Heated water from the
second pass economizer is discharged into the steam
drum. From the drum, saturated water is routed
through pipe downcomers to lower furnace enclosure
wall headers and the boiler bank. From these steam
generating circuits, the steam-water mixture is re-
turned by natural circulation to the steam drum
where the mixture is separated. From the drum,
steam-free water is again returned to the furnace and
boiler bank circuits, and water-free steam is directed
to the superheater. After flowing through the super-
heater sections, the steam leaves the recovery boiler
and is typically piped to a turbine-generator.
Boiler thermal performance

The thermal efficiency of a recovery boiler is defined
as the ratio of energy output to energy input. The
boiler output is a measure of the energy transferred Fig. 4 Typical modern recovery boiler.

The portion of the input energy available to generate

steam can be determined by calculating a steady-state
heat and material balance around the boiler. Because
steady-state output must equal the input less energy
losses, boiler efficiency can also be expressed as:
Output Input − Losses

Boiler efficiency = = (3)
Input Input
Fig. 5 illustrates the major streams crossing the heat
and material balance boundaries. The total heat in-
put can be calculated by summing the chemical and
thermal energy contained in the streams entering the
boundary. The total losses are then calculated by sum-
ming the heat losses due to endothermic reactions
occurring within the boiler and the thermal energy
losses of the exiting streams.
In practice, it is not feasible to precisely measure all Fig. 6 Determination of black liquor heat of reaction correction.
streams entering and leaving the system boundaries.
An unaccounted for heat loss and a manufacturer’s The heat of reaction correction is the difference
margin are added to the total losses to correct the cal- between the standard heat of formation of the bomb
culated efficiency for these limitations. products and the heat of formation of the furnace
The gross heating value or chemical energy of black products. Application of the heats of formation to de-
liquor is determined by combusting a black liquor termine a reaction correction is illustrated for kraft li-
sample with an excess of oxidant, under pressure, in quor in Fig. 6.
a bomb calorimeter. Under these laboratory condi-
tions, the combustion products predominantly exist as Step 1 This is the gross heating value of the black
CO 2 , H 2O, Na 2 CO 3 , Na 2 SO 4 and sodium chloride liquor sample determined in the bomb calo-
(NaCl). A key process in black liquor combustion is the rimeter.
reclamation of sodium compounds in a reduced state. Step 2 From the quantitative analysis of the fully
The reduction reactions occurring in the recovery fur- oxidized bomb calorimeter compounds, the
nace result in different combustion products than heat required to convert these products to
those resulting from the bomb calorimeter procedure. their elemental state can be calculated from
These endothermic reactions account for a portion of the the standard heats of formation of the com-
black liquor heating value that is not available in the pounds from their elements.
recovery furnace to generate steam. To accurately de- Step 3 Similarly, from the quantity of each chemi-
termine recovery boiler efficiency, the bomb calorimeter cal compound present in the furnace combus-
gross heating value must be corrected for the heats of tion products, the heat of formation for the
reaction of these different combustion products. actual furnace products can be calculated.
Fig. 5 Plant heat balance diagram. (See also Table 2.)

The difference between Step 2 and Step 3 is the heat

of reaction correction. Table 1
Sulfur dioxide (SO2 ) and Na2S are the most signifi- Black Liquor Analysis
cant recovery furnace combustion products that dif- Dry solids, % by wt
fer from those formed under bomb calorimeter condi-
tions. The heat of reaction correction for Na2S is cal- Nitrogen (N) 0.10
culated as follows: Sodium (Na) 19.77
Sulfur (S) 4.36
Na 2 SO4 = 2Na + S + 2O2 (Step 2) Hydrogen (H2 ) 3.86
Carbon (C) 35.14
(4)
2Na + S = Na 2S (Step 3) Oxygen (O2 ) 34.74
Inerts 0.30
The calculation is simplified by combining Steps 2 Potassium (K) 1.31
and 3 and using standard heats of formation: Chlorine (Cl) 0.42
Total solids 100.00
Na 2 SO4 = Na2 S + 2O2 (5) Solids gross heating value = 5985 Btu/lb (13,921 kJ/kg)
∆Hf (Na2S)
0
= 89.2 kcal/gmole
∆Hf0 (O2) = 0.0
∆Hf0 (Na2SO4) = −330.9 The black liquor gross heating value is the predomi-
Heat of reaction nant energy input to the recovery boiler system. The
correction = −241.7 kcal/gmole balance of the input is the sum of the sensible heats
= −5550.0 Btu/lb Na2S contributed by those process streams entering the
(−12,909.0 kJ/kg) boiler above a base reference temperature. The black
liquor is typically preheated to 230 to 270F (110 to
Similarly, the heat of reaction correction for sulfur 132C) prior to firing. The majority of the combustion
dioxide can be determined from standard heats of for- air (primary and secondary) is also generally pre-
mation from the bomb calorimeter combustion products: heated to promote stable furnace conditions.
Na 2 SO4 + CO2 = SO2 + Na2 CO3 + 1 O2 (6) The heat of reaction correction is expressed as a heat
2
loss due to the endothermic reduction reactions in
∆Hf0 (SO2) = 71.0 kcal/gmole calculating recovery boiler efficiency. To determine
∆Hf0 (Na2CO3) = 270.3 this heat loss, the fraction of sodium and sulfur con-
∆Hf0 (O2 ) = 0.0 verted to Na2S, Na2SO4 and SO2 must be calculated
∆Hf0 (Na2SO4 ) = −330.9 from the chemical analysis of the smelt and flue gas
∆Hf0 (CO2 ) = −94.1 leaving the recovery boiler. For the example presented
Heat of reaction in Table 2, 0.099 lb of Na2S is formed for each pound
correction = −83.7 kcal/gmole of black liquor solids entering the recovery boiler. The
= −2360.0 Btu/lb SO2 heat of reaction correction or heat loss associated with
(−5489.0 kJ/kg) the formation of Na2S is calculated as follows:
In actual furnace operations, there is a variety of par- 0.099 lb Na 2S 5550 Btu 250, 000 lb solids
tially reduced, partially oxidized combustion products. × ×
However, accounting only for the presence of SO2 and lb solids lb Na2S h
(7)
Na2S in correcting the bomb calorimeter gross heat- = 137.36 × 106 Btu/h
ing value closely approximates black liquor combus-
tion in a recovery furnace. In addition, 0.0017 lb of SO2 is formed in the re-
Salt cake makeup and other additives to the black duction of Na2SO4 to Na2CO3:
liquor are treated in a manner similar to the heat of re-
action correction in calculating recovery boiler efficiency. 0.0017 lb SO2 2360 Btu 250, 000 lb solids
The heat of formation or gross heating value of the × ×
Na2SO4 salt cake is accounted for as a contribution to the lb solids lb SO2 h
(8)
total system energy input. The subsequent reduction of = 1.0 × 106 Btu/h
Na2SO4 to Na2S and O2 is then taken as a heat loss.
The black liquor elemental analysis and gross heat- The heat loss due to the reduction reactions is the sum
ing value are used to determine the chemical and ther- of these heat of reaction corrections:
mal performance of the recovery boiler. A typical black Reduction reaction heat loss =137.36 × 106 + 1.0 × 106
liquor analysis is presented in Table 1. =138.36 × 106 Btu/h
Table 2 lists the inputs and losses for a recovery unit
firing 250,000 lb/h (31.5 kg/s) dry solids at 70% black In addition to the heat of reaction correction and
liquor concentration based on the composition and the heat loss attributed to reducing salt cake makeup,
heating value given in Table 1. Industry practice is energy is lost from the boiler in the form of sensible
to express the various heat losses as a percentage of heat. Heat is also lost through water vaporization and
the total heat input, also shown in Table 2. The sys- through the molten smelt. Typically, smelt leaving the
tem boundaries for the heat and material balance are recovery furnace represents 532 Btu/lb (1237 kJ/kg)
shown diagrammatically in Fig. 5. of heat consumed to melt the smelt and raise its tem-

factors result in an increased quantity of theoretical

Table 2 air (see Chapter 10) required to combust the black li-
Material and Energy Balances for a Recovery Boiler Firing quor. The overall trends can be summarized as follows:
250,000 lb/h Dry Solids at 70% Liquor Concentration
1. Carbon (and hydrogen) content increases with in-
Material balance: creasing heating value.
Entering combustion air = 1,176,620 lb/h 2. Inorganic sodium and sulfur contents decrease
Entering infiltration air = 20,550 lb/h with increasing heating value.
Entering black liquor = 357,143 lb/h 3. Theoretical air increases with increasing carbon
Total in 1,554,313 lb/h and hydrogen contents.
Smelt leaving = 111,200 lb/h 4. Theoretical air increases with increasing heating
Wet gas leaving = 1,442,290 lb/h value.
Particulate leaving = 823 lb/h These trends can be used as quick checks on labora-
Total out 1,554,313 lb/h
tory results for a given black liquor sample chemical
Energy balance: 106 Btu/h % Total analysis and gross heating value.
Chemical heat in liquor = 1496.25 94.50
Sensible heat in liquor = 37.47 2.37
Sensible heat in air = 49.59 3.13 Black liquor as a fuel
Input 1583.31 100.00
Sensible heat in dry gas = 101.49 6.41
Black liquor
Moisture from air = 2.37 0.15 Black liquor is a complex mixture of inorganic and
Moisture from hydrogen = 104.82 6.62 organic solids partially dissolved in an aqueous solu-
Moisture from liquor = 129.20 8.16 tion. Heavy or strong black liquor introduced to the
Reduction reactions = 138.36 8.74 recovery furnace ranges from 60 to 80% solids by
Heat in smelt = 71.25 4.50 weight. The organic fraction of the solids is principally
Radiation = 4.75 0.30
Unaccounted for and
derived from the hemicellulose and the lignin removed
manufacturer's margin = 15.83 1.00 from the cellulose strands of the wood chips. The solids’
Losses 568.07 35.88
inorganic fraction is primarily Na 2 CO 3 , sodium
hydrosulfide (NaHS) and oxidized sulfur compounds.
Boiler efficiency = Black liquor also contains various chemical elements
which enter the process with the wood, as impurities
Input − Losses 1583.31 − 568.04
= = 64.12% in makeup limestone and salt cake, and as contami-
Input 1583.31 nants in makeup water. These elements include po-
Output = Efficiency x Input =
tassium, chlorine, aluminum, iron, silicon, manganese,
magnesium and phosphorous. The waste stream from
64.12 6
x 1583.31 x 106 = 1015.22 x 10 Btu/h a chlorine dioxide generator in a bleached mill can also
100 contribute NaCl. Potassium and chlorine directly im-
Steam flow = pact the recovery boiler design and operation if they
are present in the black liquor in sufficient quantities.
Output 1015.22 x 106 It is not uncommon for many other waste streams
= = 847,970 lb/h
Hs − Hfw (1444.16 − 246.93) and effluents from the mill to be added to the black li-
quor. This may include soap, various brines or other
effluents from the bleach plant, or a variety of other
perature to a nominal 1550F (843C). The balance of streams. These may significantly affect the chemical com-
the heat losses are determined in a manner similar to position or heating value of the black liquor fuel, which
those for conventional power boilers. (See Chapter 22.) can have major impacts on performance, operations,
The contribution to boiler efficiency offered by the emissions and/or cleanability of the recovery boiler.
remaining streams crossing the recovery unit heat and Black liquor is sprayed into the furnace as coarse
material balance is primarily established by their sen- droplets which fall to the floor in a dry and partially
sible heat content at the temperature at which they combusted state to form a char bed. The mounded bed
cross the system boundary. The minimum tempera-
ture of the flue gas leaving the boiler is selected to
minimize corrosion. The heat transfer surface arrange-
ment and thermodynamic considerations then dictate
the economic limit for the flue gas exit temperature,
typically 350 to 400F (177 to 204C).
The gross heating value of a given black liquor
sample is strongly influenced by its carbon content.
As this content increases, the heating value typically
increases, as illustrated in Fig. 7. An increased liquor
heating value also generally corresponds to an in-
creased hydrogen content, with a corresponding de- Fig. 7 Black liquor high heating value as a function of carbon
crease in inorganic sodium and sulfur contents. These content in dry solids.

consists of a matrix of carbon and inorganic sodium 350

chemicals rising 3 to 6 ft (0.9 to 1.8 m). The black li-
quor droplets sprayed into the furnace must be large 300
Lower Solids
Black Liquor
enough to minimize droplet entrainment in the rising (<70% Solids)
combustion gases, yet small enough so that they fall
Sulfur Dioxide (at 8% O ), ppm

to the bed nearly dry. Wet liquor droplets reaching the 250
bed can quench the burning char and cause a bed
blackout, or can result in high sulfur emissions. 200
The design of the recovery furnace must promote
combustion of the black liquor in parallel with the
efficient reduction of sodium compounds. The absolute 150
reduction efficiency is determined by the degree, on a
weight percent, to which sulfur is present in the smelt 100 Higher Solids
in a reduced state, such as Na2S and NaHS. Black Liquor
(>70% Solids)
Reduction efficiency = 50
Na 2 S + NaHS
× 100%, Na 2O (9)
Total sodium sulfur compounds 0
14 18 22 26 30 34 38 42
Smelt Sulfidity, %
A common industry simplification is as follows: Na2S
Where Smelt Sulfidity is Percentage Ratio (weight, %) of:
Na2S + Na2CO3 + NaOH
Reduction efficiency = Expressed as Na2O in the Smelt
Fig. 8 Sulfur dioxide emissions.
Na 2 S (10)
× 100%, Na 2O
Na 2 S + Na2 SO4
sulfidity. An environmental benefit of increased black
The industry practice is to express the compounds liquor concentrations fired in recovery boilers is a re-
in the equations as the equivalent weight of Na2O. duction in SO2 emissions.
Concentrations of TRS in the combustion gases
Emissions leaving a modern boiler are readily controlled below
The black liquor combustion process is never theo- 5 ppm, as the H2S and volatile organic sulfide com-
retically complete. This results in small concentrations pounds are oxidized in the high temperature furnace.
of unburned combustibles, typically carbon monoxide VOC and CO emissions can be controlled by proper
(CO), organic and sulfur compounds, and hydrogen furnace design and operation. VOC can be maintained
sulfide (H2S), being discharged to the atmosphere. The below approximately 80 ppm (current Environmen-
volatile organic compounds, or VOC, are generally tal Protection Agency/EPA limit) while CO emissions
expressed in terms of equivalent methane (CH4) and are controllable to less than 500 ppm. A hot furnace
are sometimes more specifically referred to as and thorough mixing of combustion air with the gen-
nonmethane volatile organic compounds (NMVOC). erated volatiles are essential in minimizing VOC, TRS
H2S and sulfur-bearing organic compounds such as and CO emissions. Particulate is removed from the
mercaptans are grouped together as total reduced sul- combustion gases in a high efficiency electrostatic pre-
fur (TRS). Trace amounts of SO2 also exist in addition cipitator, which can control the stack discharge par-
to TRS-bound sulfur. As in most combustion processes, ticulate to the current EPA limit of 0.044 gr/dscf.
nitrogen oxides (NOx) are present and are expressed in
terms of equivalent nitrogen oxide (NO2). Black liquor Ash
combustion also creates particulate matter. Ash accumulations on heat transfer surfaces cre-
The modern recovery boiler achieves effective NOx con- ate an insulating barrier that reduces heat transfer
trol by staged air combustion, control of excess air, and a to the boiler tubes. Consequently, as the ash deposits
uniform distribution of the black liquor through multiple build and heat transfer decreases, steam outlet tem-
burners. A recovery furnace inherently produces lower peratures decay and the flue gases retain higher tem-
NOx emissions compared to fossil fuel boilers. Burning 68 peratures as they pass through the boiler surfaces.
to 75% solids concentration black liquor, NOx levels Higher flue gas temperatures lead to more ash in its
would normally be expected to be below 100 ppm. molten phase being carried further back in the boiler
Recovery boilers can often be upgraded in capacity convection pass where it adds to already present ac-
with little or no increase in NOx emissions, as air port cumulations. As ash deposits grow, they also begin
sizes and locations can be modified to allow adequate restricting gas flow through the boiler, plugging the
control of operations, and emissions, when increasing gas passes, and eventually increasing the furnace
solids input. Numerical modeling of the existing air draft loss to inoperable levels.
system using actual operating data provides the engi- The characteristics of ash from black liquor combus-
neer with accurate predictions of NOx and particulate tion impact the design of the process recovery boiler.
emissions before hardware is installed. Approximately 45% by weight of the dry, as-fired sol-
SO2 emissions are a function of the sulfidity of the ids is inorganic ash. The majority of these inorganics
smelt. Fig. 8 shows the general variation of SO2 with are removed from the furnace as Na2S and Na2CO3 in

the molten smelt. A significant amount of ash is stack. More fuming than that sufficient to capture the
present as particulate entrained in the existing flue sulfur causes the excess alkali to be converted to car-
gases. Generally, about 8% by weight of the entering bonate in the ash. Less fuming than that sufficient to
black liquor dry solids leaves the furnace as ash. capture sulfur causes excess sulfur to be released as SO2,
Ash is generally categorized as fume or carryover. and chlorine to be released as HCl in the stack gas,
Carryover consists of char particles and black liquor rather than being converted to chloride in the ash.
droplets that are swept away from the char bed and As potassium (K) has a higher vapor pressure than
liquor spray by the upward flue gas flow. Entrain- sodium (Na), the fume contains a higher ratio of K/
ment occurs when small particles caught in the fur- Na than that found in smelt or black liquor. This is
nace gases are not of sufficient size, shape or density referred to as potassium enrichment. Chlorides are also
to fall back into the furnace. Entrainment results in found at higher concentrations in fume. Potassium and
combustion of black liquor in the upper furnace which chlorides can contribute to severe plugging in the re-
affects temperature and ash deposit properties. En- covery boiler convection surfaces.
trainment of smelt and char materials is a major cause Ash fouling and gas path plugging within recov-
of convection surface plugging. ery boilers are directly related to the melting proper-
Once entrained, the black liquor carryover droplet ties of the ash in the boiler. Chloride and potassium
follows the gas flow. When complete particle burnout concentrations within the liquor cycle are the most sig-
occurs, the entrained droplet can settle out of the gas nificant factors affecting ash melting points. High
flow as a smelt bead. Otherwise, the partially com- chloride concentrations are the result of high chloride
busted particles form sparklers that deposit on tubes sources such as in the wood supply or makeup chemi-
as char, then continue to burn and yield a smelt de- cals. Environmental improvements within the last
posit. At low loads with lower furnace gas flow rates, decade have reduced chemical losses throughout the
entrained droplets have time to burn out, and only system, and increased various dead-load chemicals,
small smelt droplets show up as carryover. As load is including chlorides, within the liquor stream.
increased, larger drops can be entrained by the cor- One of the main factors in determining ash deposi-
respondingly increased gas flow. The particles can tion rates is the ash stickiness.3 Ash stickiness is a func-
then include small smelt droplets and large char par- tion of the amount of liquid phase present in the ash,
ticles. Carryover can be controlled by furnace size and that is dependent upon ash chloride content and tem-
by proper design and operation of the firing and com- perature.
bustion air systems. A simplified relationship between the ash chloride
Fume consists of volatile sodium compounds and content and the sticky temperature is shown in Fig.
potassium compounds rising into the convection sec- 9. This graph may be used to illustrate the anticipated
tions of recovery boilers. These volatiles condense into effects of elevated ash chloride levels in general terms.
submicron particles that deposit onto the superheater, The conditions of this particular graph are at a 5%
boiler bank and economizer surfaces. Fume particles potassium molar ratio. Notice that the sticky band on
in kraft recovery boilers are usually 0.25 to 1.0 mi- this graph covers the widest temperature range from
crons in diameter and consist primarily of Na2SO4 and 5 to 10% molar chloride levels and would be in a nar-
a lower content of Na2CO3. Fume also contains potas- row range at higher and lower chloride levels.
sium and chloride salts. Ash enrichment by chloride reduces the ash melt-
The much larger carryover particles, typically greater ing point and increases the deposit sintering rate. The
than 100 microns, are easily distinguishable from the characteristic sticky temperature has been defined as
submicron fume particles. Fume and carryover ash are the temperature where 15% of the alkali salt mixture
also different in their chemical analyses. Carryover is is liquid. The presence of K in combination with chlo-
similar in composition to the smelt (see comments above). rides further reduces the sticky temperature of depos-
Fume is mostly Na2SO4 and is enriched in potassium and
chloride relative to their concentration in the smelt. 850
Fume can contribute to deposit formation and plug-
ging in the convection heat transfer sections of the 800 Radical
5 Mole% K/(Na+K)
boiler, particularly if allowed to sinter and harden. Deformation

Fume particles are also the predominant source of 750 Slagging
particulate emissions from recovery boiler stacks.
A third category of ash is represented by interme- 700
Temperature, C
diate size particles (ISP), a class of particles between

carryover (> 100 microns) and submicron fume, which 650 Sticky
are produced during combustion of black liquor drop- Not
lets and the char bed. While ISPs are abundant, ex- 600 Sticky
ist everywhere, and are potentially important to foul-
ing in recovery boilers, the mechanisms by which these 550
First Melting
particles are formed are not yet well understood.
Char bed temperature controls the fuming rate. A 500
rate just sufficient to capture the sulfur released dur- 0 2 4 6 8 10 12 14 16 18 20
ing combustion should be established. This minimizes CI/(Na+K) Mole %
the dust load to the precipitator and the SO2 to the Fig. 9 Sticky temperature.4

its. The recovery boiler should be designed to reduce in cooperation with B&W, was installed at Windsor
the gas temperature entering the boiler bank to be- Mills in 1934. The water-cooled design was a complete
low the ash sticky temperature to avoid bank plug- success, and the boiler operated until 1988. The first
ging. Decreasing the Cl level in the black liquor can Tomlinson recovery boilers in the U.S. were two 90
also decrease the plugging tendency of the resulting B&W-Btu t/day units sold to the Southern Kraft Cor-
ash. The successful reduction of chloride levels has poration in Panama City, Florida in 1935.
been achieved by ash purging. When purging ash (see The Tomlinson design evolved with a technique of
Ash system), ash is removed periodically to maintain spraying black liquor onto the furnace walls. The li-
chloride levels at a specified target. For the most part, quor is dehydrated in flight and on the furnace walls,
maintaining a chloride level in the precipitator ash of where pyrolysis begins with the release of volatile
1.5% or less has proven to be successful in reducing foul- combustibles and organically bound sodium and sul-
ing and plugging within recovery boilers. fur. As the liquor mass builds on the furnace walls,
its weight eventually causes it to break off and fall to
the hearth. There, pyrolysis is completed and the char
Recovery boiler design evolution is burned, providing the heat and carbon required in
The kraft recovery process evolved in Danzing, the reduction reaction.
Germany approximately 25 years after the soda pro- By the end of World War II, the recovery boiler de-
cess was developed in the United Kingdom in 1853. sign (Fig. 11) had evolved to the general two-drum
In 1907, the kraft recovery process was introduced in arrangement that represented B&W’s standard prod-
North America. From its inception, a variety of fur- uct until the mid-1980s. Retractable sootblowers us-
nace types competed for a successful commercial de- ing steam as a medium eliminated hand lancing in the
sign, including rotary and stationary furnaces. Dur- 1940s; this significant development made large recov-
ing the late 1920s and early 1930s, significant design ery boiler designs practical.
developments were achieved by G.H. Tomlinson,
working in conjunction with B&W engineers.
The first Tomlinson recovery boiler was supplied by
B&W Canada in 1929, at the Canada Paper
Company’s Windsor Mills, Quebec plant (Fig. 10). This
black liquor recovery boiler had refractory furnace
walls that proved costly to maintain. The steam gen-
erated with the refractory furnace was also much less
than that theoretically possible. Tomlinson decided that
the black liquor recovery furnace should be completely
water-cooled, with tube sections forming an integral
part of the furnace. This new concept boiler, designed
Fig. 10 First Tomlinson recovery boiler. Fig. 11 General two-drum arrangement of the 1940s.

Wall and floor construction sion protection. Lower furnace protection should be
By 1946, furnace wall construction had evolved determined from criteria such as steam pressure, the
from tube and refractory designs to a completely wa- history of furnace corrosion, capital budget, and main-
ter-cooled furnace enclosure, using flat plate studs to tenance expectations. The list of common means of
close the space between tubes and to minimize smelt protection includes chromized carbon steel tubes,
corrosion and the resultant smelt leaks. The flat stud chromized pin studs, carbon steel pin studs, metallic
design was superseded in 1963, with membrane tube spray coatings, high density pin studs, 304L, Alloy 825
construction where the gas-tight seal is along the plane and Alloy 625 composite tubes, and weld overlay of
of the wall rather than formed by casing behind the wall. carbon steel tubes. Normally, carbon steel tubes are
The 1963 furnace wall construction had 3 in. (76 used below 900 psig (6.2 MPa) and tubes with an al-
mm) outside diameter (OD) tubes on 4 in. (102 mm) loy outer surface are used above this pressure.
centers. The advantages of this construction included A new or rebuilt high pressure recovery boiler may
less air infiltration, reduced refractory maintenance, have several different tubes in the lower furnace (see
and a completely gas-tight unit. The design used cy- Fig. 12). The floor may be carbon steel with pin studs.
lindrical pin studs for corrosion protection of the tubes To provide additional circulation margin in the floor,
in the reducing zone of the lower furnace. The pin and protect against extreme heat absorption upset
studs held solidified smelt, forming a barrier to the conditions, the use of multi-lead ribbed (MLR) tubing
corrosive furnace environment. The current construc- has become common, and has become the norm in
tion calls for 64 half-inch (13 mm) diameter studs per carbon steel floors regardless of whether the floor is
linear foot (0.3 m) of tubing. sloped or flat. It is also common for carbon steel floors
The lower furnace design continued to evolve in the to use tubes with an alloy outer surface for the first 3
1980s from the traditional pin stud arrangement to ft (0.9 m) from each side wall, as these tubes can have
the use of composite or bimetallic tubes. The compos- accelerated corrosion rates over the remainder of the
ite tubes are comprised of an outer protective layer of floor due to the continued exposure to molten smelt.
AISI 304L stainless steel and an inner core layer of The vertical walls from the floor to an elevation above
standard American Society of Testing and Materials the primary air port elevation would normally be 825
(ASTM) A 210 Grade A1 carbon steel. The composite composite or 625 weld overlay. Above this elevation,
tube inner and outer components are metallurgically up to approximately 3 to 15 ft (0.9 to 5 m) above the
bonded. The outer layer of austenitic stainless steel, tertiary air ports (or quaternary zone), 304L can be
which is also used to cover the furnace side of the car- used to reduce costs.
bon steel membrane bar, protects the core carbon steel Materials continue to be studied and evaluated in
material from furnace corrosion. the laboratory and in operating recovery boilers for
Not long after the introduction of 304L composite corrosion protection.
tubes, issues with sodium hydroxide attack of the
stainless layer near air ports, and cracking of the 304L
layer and tube-to-membrane weld, were discovered.
The cracking and corrosion have typically been spe-
cific to the floor and primary air ports. Considerable Enhanced
investigation has occurred with other materials iden- Tube Materials
or Bare
tified as probable substitutes for 304L. Differential Carbon Steel
expansion of the two layers has been identified as an
issue. Table 3 shows the coefficients of expansion and
tensile strength for different materials commonly used
to protect recovery boiler lower furnace tube surfaces.
Several methods are used for lower furnace corro-
Coextruded 304L
(>900 psig/6.2 MPa)
Table 3
Properties of Materials Used to Protect Carbon Steel
with Pin Studs
Recovery Boiler Lower Furnace Tube Surfaces (<900 psig/6.2 MPa)
Carbon Type Incoloy Inconel

Property Steel 304L 825 625
Expansion coefficient Alloy 625, 825

(>900 psig/6.2 MPa)
Mean to 700F (371C) x
Carbon Steel
10−6 (in./in. F) 7.59 9.69 8.3 7.5 with Pin Studs
(<900 psig/6.2 MPa)
Thermal Conductivity
at 700F (371C) Alloy 625, 825
(Btu/h ft2 F) 320 142 115 117 Smelt Runs
Carbon Steel
Ultimate Tensile Strength with Pin Studs
ksi at 1000F (538C) 56 86 132
Fig. 12 Material zones in lower furnace.

Increased industry emphasis on high pressure and a wider 10 in. (254 mm) side spacing to alleviate this
temperature operation, along with the higher avail- pluggage potential.
ability demanded of large boilers and the trend of In the 1980s, a corrosion phenomenon was discov-
many mills being dependent upon a single recovery ered in the lower portion of the generating bank just
boiler, have required the decreased maintenance af- outside the lower drum. Near-drum corrosion could
forded by modern composite tubes. The single-drum result in rapid corrosion of the generating bank tubes
boiler designed in 1987 featured readily available 2.5 immediately above the lower drum surface. The cor-
in. (64 mm) OD composite tubes with 0.5 in. (13 mm) roded area is typically 0.25 to 0.50 in. (6 to 12 mm) in
wide membrane bars. Fig. 13 chronicles the evolution diameter and can be located 180 degrees apart on the
of furnace wall construction with the decreasing width sides of the tubes. The corrosion is normally within 1
between tube seal bars. in. (25 mm) of the lower drum top surface. The corro-
sion rate can be very high and is identified through
Two-drum generating bank ultrasonic testing of the tubes from inside the lower
The two-drum generating bank has evolved from drum. In 2001-2002, B&W developed and patented a
a multi-pass design to a single pass design, common new product called GenClad® to protect the carbon steel
since the early 1960s. The multi-pass design gener- tube surface immediately above the lower drum (see
ally had two flue gas passes, with the gases entering Fig. 14). The generating bank tube is coated with
the bank near the top, being directed downward with 309H stainless steel, approximately 0.050 in. (1.27
a tile baffle wall integral to the bank, then turning mm) thick, using a laser fusion method. The tube is
and flowing upward, exiting the bank near the top then swaged to reduce the tube outside diameter to
and flowing out to the economizer. match the drum hole and the cladding is smoothed in
In the 1960s, the generating bank became a single the process, ready for rolling into the lower drum. The
gas pass bank. The flue gas enters and traverses the cladding is put on the tube in an area that is swaged
entire generating bank height in one horizontal and is extended into the gas stream several inches to
crossflow pass to the outlet flue. The tube spacing is 5 provide protection from near-drum corrosion.
in. (127 mm) side spacing using 2.5 in. (64 mm) tubes.
The generating bank screen, tubes between the su- Evolution of the modern, single-drum design
perheater and generating bank, was also originally The 1980s saw an increase in the pulp and paper
on 5 in. (127 mm) side spacing and became an area industry’s need for high pressure and temperature
for pluggage, especially when the original capacity of steam generation from the recovery boiler. This trend
the recovery boiler was exceeded. Today, an existing was paralleled by the demand for large, conservatively
generating bank screen can be rearranged to provide sized furnaces and general acceptance of the single-
drum, all welded boiler design. B&W commissioned its
first modern single-drum boiler in 1989, at Gaylord
Container Corporation in Bogalusa, Louisiana.
In the two-drum design arrangement, the drums
are exposed to combustion gases which limit the drum
length that can be effectively supported. This maxi-
mum length established the design capacity of the two-
drum arrangement at about 5 × 106 lb (2.3 × 106 kg)
of dry solids per day. In the single-drum arrangement,
the steam drum is moved out of the gas flow path,
thereby removing this limitation and allowing recovery
boilers designed to process daily solids rates of up to 9 to
10 × 106 lb (4.1 to 4.5 × 106 kg) of dry solids per day.
Black liquor solids concentration
The air pollution legislation of the mid-1960s forced
major changes in recovery boiler design. To reduce
malodorous emissions, the direct contact evaporator
was replaced by additional multiple effect evaporator
capacity to obtain the optimum liquor concentration.
Economizer surface was added for flue gas cooling that
was previously accomplished in the direct contact
evaporator.
Floor design
There are two generally accepted floor arrange-
ments for recovery boilers: a full sloped floor design
and a flat or decanting style. The full sloped design
slopes the entire floor at 4 to 6 degrees, and is intended
to produce an arrangement that results in a complete
Fig. 13 Evolution of wall construction. drainage of the smelt. The flat or decanting style has

tainer Corporation) in Hodge, Louisiana; it generated

steam at 1250 psig (8.6 MPa) and 900F (482C).
B&W’s high steam temperature design philosophy
is reflected in the arrangement of superheater surface.
The inlet primary superheater bank is placed follow-
ing the furnace cavity, with steam flowing through
the bank parallel to the gas flow. This results in the
Lower coolest available steam flowing through the super-
GenClad
Drum Protective heater tubes exposed to the hottest gas temperatures
Layer and the radiant heat from the furnace. This arrange-
ment minimizes the metal temperature of the super-
heater tubes.
Early recovery boilers had front superheater sec-
tions spaced on 10 in. (254 mm) side spacing and rear
sections spaced on 5 in. (127 mm) side spacing. This
arrangement was used when the furnace construction
Lower
Drum
Fig. 14 Carbon steel tube surface protected with GenClad®.

Burners
little or no slope, and is intended to maintain a pool of Secondary

smelt in the lower furnace. B&W traditionally provided Air Ports
only the sloped floor for all two-drum units and all
single-drum units. Sloped tubes provide positive cir- Primary
culation and greater margin for waterside operational Air Ports
upsets in this high heat input area of the furnace.
Floor arrangements are shown in Fig. 15.
Flat or decanting floors may be modified to incor-
porate some sloping capabilities, primarily at the front
and rear of the furnace and along the side walls. B&W
has a dual-sloped dihedral design, sloped at the sides,
which can increase flow and circulation margin when
conditions require. From an operational standpoint,
the sloped or decanting styles allow some inventory Sloped Furnace Bottom
of smelt in the lower furnace. Some operators feel this
improves operation and reduces smelt spout and open-
ing issues. Existing fully-sloped floors may be modi-
fied to achieve a partial decanting effect by dual slop-
ing the floor from the front and rear. This provides
the desired smelt inventory while maintaining sloped
tubes for circulation. Smelt spouts may also be raised
slightly above the floor level to provide a pool of mol-
ten smelt immediately in front of the smelt openings. Burners
Lower furnace floor support design has evolved over Secondary

the years. Floor beams under the floor tubes have in- Air Ports
creased in number to help strengthen the floor and
Primary
reduce the potential for damage that can result from Air Ports
heavy salt cake falls from the upper furnace eleva-
tions. Floor beam end connections at the side walls
have been redesigned for additional strength, to hold
side walls against the floor in the event of a major
furnace upset or explosion. These improvements have
led to a more rigid design able to withstand a variety
of operational conditions.
Superheater design
B&W’s first recovery boiler designed for elevated pres-
sure and temperature was placed in operation in 1957, Decanting Floor
at Continental Can Company (now Smurfit-Stone Con- Fig. 15 Recovery boiler floor arrangements.

was 3 in. (76 mm) tubes on 5 in. (127 mm) centers. ciency), and reliability. There are several current designs
The closer spaced 5 in. (127 mm) side spaced sections which meet the needs of the industry (see Fig. 16).
may be modified to 10 in. (254 mm) side spacing to The close side-spaced, horizontal, continuous-tube
alleviate a potential pluggage area, particularly at economizer was an early design used to reduce the
higher loads. When these superheater components are temperature going to the direct contact evaporator or
replaced for any reason, consideration should be given air heater. To keep gas temperatures high for the di-
to make the banks consistent with all 10 in. (254 mm) rect contact evaporator or air heater (600F/316C or
side spacing. This may require a change in super- greater), the economizer was small. This economizer
heater surface area, but will result in a superheater was always a crossflow arrangement with the gases
that offers improved cleanliness. flowing perpendicular to the tube surface. This was
Ash buildup and superheater surface plugging have an efficient method of heat absorption, but presented
frequently limited availability of the recovery boiler. To a cleaning problem. Instead of sootblowers, B&W de-
avoid these conditions, in 1968 B&W established a 12 veloped and used shot systems for cleaning gas side
in. (305 mm) side spacing for the entire superheater deposits. This system took small pieces of metal, such
bank, abandoning the conventional 5 and 6 in. (127 as blanks from the manufacture of nuts and bolts, and
and 152 mm) spacing in the secondary superheater con- dropped them across the economizer surface. The shot
struction. This increased the clear side spacing in the was collected in a hopper and returned to drop on the
superheater from 3.5 to 9.5 in. (89 to 241 mm). economizer surface. This was done repeatedly to clean
Superheater tie arrangements have evolved as tube any salt cake deposits from the outer surface of the
backspacing has changed and improved surface con- tube. This method of cleaning was not as effective as
figurations have been adopted. Pendant superheat- sootblowing and presented problems with both the
ers (see Fig. 18) have utilized D-links or tongue and return system and tube damage over time.
groove ties in the fore and aft direction. The tongue and When direct contact evaporators were discontinued,
groove tie allows for greater tube differential expansion the economizer size needed to increase. The gas tem-
and improved welding capabilities. Platen superheaters perature exiting the direct contact evaporator is nor-
(see Fig. 18) have used pin and pipe ties, or a slip spacer mally around 400F (204C) and a new, larger econo-
type of tie, to restrain the tubes. mizer was designed to provide the same exit tempera-
ture. Gas flow across the tubes (perpendicular) was
Economizer design maintained due to its efficient heat transfer, but to
The recovery boiler economizer has evolved several accommodate the increased economizer size necessary,
times over the years in response to the change to low odor the economizer arrangement was changed to vertical
operation, cleanliness, increased heat utilization (effi- tubes with multiple (three or five) crossflow gas paths.
Boiler
Bank
Boiler
Gas Bank
Inlet
Gas Flow
Gas Gas
Inlet Inlet
Water
Outlet
Water
Inlet Gas
Outlet
Gas Gas
Gas Outlet Outlet
Outlet
(a) Horizontal (b) Five-Pass Crossflow (c) Longflow (d) Three-Pass

Cascading Longflow
Fig. 16 Recovery boiler economizer arrangements.

The five-pass bare tube economizer design contained ing boilers. Several features resulting from this devel-
much greater heating surfaces than would have been opment program include the use of variable velocity
available with the close side-spaced horizontal surface, control dampers on the secondary and tertiary air
and was designed to improve gas-side cleanliness. ports to better regulate air penetration across the fur-
As new recovery boilers became larger in capacity nace area, an interlaced port arrangement to provide
or existing boilers underwent capacity increases, the better gas mixing within the furnace, and optimiza-
higher flue gas quantities, velocities and carryover tion of port location.
made cleanliness an issue. This promoted the devel-
opment of the longflow economizer (Figs. 4 and 20).
The longflow economizer is a two gas/two water pass Design considerations for B&W
arrangement that has some limited amount of recovery boiler
crossflow surface at entrances and exits of the banks,
but primarily relies on the parallel flow of gases across
the tubes for heat transfer. Because the flow of gases Furnace design
parallel to tube surfaces is less efficient than gas flow The design of the modern recovery boiler and its
across tubes, longitudinal fins were added to the tube associated equipment systems must first consider ef-
to enhance the effective tube surface area and im- ficient black liquor combustion.
prove heat transfer. Minor revisions have occurred to The overall black liquor composition (chemistry,
the longflow economizer over the years to make all percent solids, and heating value) determines how the
tubes straight along with improving the tie design and liquor dries in the furnace. Some compositions of li-
arrangement. Water flow is always from bottom to top. quor characteristics (higher solids and heating values)
The economizer bank closest to the gas outlet is the first are more conducive to in-flight, suspension drying of
water pass. The feedwater enters the bottom of this the droplets, while other characteristics (lower heat-
bank, exits the top, and is piped to the bottom of the ing values or solids) may require additional droplet dry-
bank closest to the generating bank. The water exits ing time. In these instances, spraying liquor on the
the top of this second water pass and is directed to the walls between the secondary and tertiary air port lev-
steam drum. els can provide greater dehydration prior to falling onto
Space may sometimes be limited for a longflow econo- the hearth char bed. Flexibility in operating parameters
mizer retrofit without major building modifications. An (combustion air quantities, distribution and tempera-
alternative finned tube design was developed by B&W tures, liquor spray methods and characteristics) is re-
for this condition, the three-pass cascading longflow quired to accommodate potentially varying conditions.
arrangement. This design incorporates considerable Primary air enters the furnace around the perim-
crossflow effectiveness while opening up the bank to eter of the hearth bed. The controlled reducing atmo-
reduce gas-side velocity and improving the overall sphere at the hearth burns the char at the bed sur-
cleanliness. face to maximize reduction of Na2SO4 to Na2S in the
The horizontal continuous tube economizer was re- smelt. The remaining air is admitted at the second-
introduced in a version that has increased the tube ary and tertiary air zones. The total air admitted
spacing and provided for effective sootblowing. This through the primary and secondary air ports is ap-
economizer can be supplied when space limitations proximately the stoichiometric requirement for black
dictate a more compact design to reduce building modi- liquor combustion. High pressure air entering through
fications. It is used primarily when large regenerative large secondary ports penetrates across the furnace
air heaters are replaced with an economizer. to assure mixing with the volatile gases rising from
The choice of economizers for retrofitting existing the char bed. Combustion at the secondary air level
recovery boilers should be made by the boiler designer, achieves a maximum furnace temperature zone be-
working with the mill and the existing arrangement. low the liquor spray for drying the liquor. Secondary
New recovery boilers will be arranged with straight air also limits the height of the char bed by providing
tube longflow designs, while retrofits may use any of the air for combustion across the bed surface.
designs identified in the evolution discussion. Regard- Further turbulence and mixing are created by ad-
less of arrangement, the economizer must have good mission of tertiary air, which assures complete com-
sootblower coverage and personnel access for inspection. bustion of unburned gases rising from the secondary
zone and of volatiles escaping from the sprayed liquor.
Combustion air system Tertiary air mass penetration also provides a uniform
The first recovery boiler to introduce air at three temperature and velocity profile of combustion gases
furnace levels – primary, secondary and tertiary – was entering the convection surface. Quaternary air is a
built by B&W in the late 1940s. In 1956, a concen- fourth level of air which is sometimes applied above
trated development effort was successful in providing the tertiary zone. Quaternary air has been shown to
fuller utilization of tertiary air, which had been largely lower NOx and particulate emissions, and is being
ineffective in earlier designs. Today’s advanced air applied to recovery boilers in original design or as ret-
management system is a result of extensive labora- rofits and upgrades.
tory scale and computer flow modeling, theoretical The recovery boiler furnace must also be designed
consideration for the air penetration across the fur- for efficient removal of the molten inorganic chemi-
nace at the secondary and tertiary air levels, and test- cals as smelt. Finally, the combustion gases and par-
ing of different air system configurations on operat- ticulate carryover must be adequately cooled in the

furnace to minimize deposition on convection surfaces.

The first step in the design of a new recovery boiler
is the selection of furnace plan area, defined as the
furnace width times depth. The plan area is gener-
ally set to achieve a black liquor solids heat input of
900,000 to 950,000 Btu/h ft2 (2.83 to 2.99 MW/m2). As
the solids heating value decreases, a larger furnace
plan area is desirable. However, an oversized plan
area can lead to local cold spots on the smelt bed, which
in turn limit reduction efficiency. Cold spots can also
lead to unstable furnace blackouts. A large plan area
further constrains load turndown with stable combus-
tion. An undersized plan area generally leads to in-
creased fume and particle carryover.
Once the plan area is established, the width and
depth dimensions are selected. Maintaining a depth Fig. 17 Burner and secondary air port windbox attachments.
to width ratio between 1.0 and 1.15 allows an effec-
tive arrangement of the combustion air ports and gen-
erally permits an economical arrangement of convec- the gas to temperatures where sootblowers can effec-
tion pass heat transfer surfaces. In smaller recovery tively remove the chemical ash from convection surfaces.
furnaces designed for high steam temperature, a The furnace arch, or nose, serves several important
higher aspect ratio permits increasing the depth to functions. The arch shields the superheater from the
accommodate the large superheater surface. Furnace radiant heat of the furnace. The high temperature
height is then determined by the radiant furnace heat steam loops of the superheater are completely pro-
transfer surface required to cool the combustion gases tected. Penetration of the arch into the furnace uni-
below 1700F (927C). formly distributes the gas entering the superheater.
The surface of the floor and wall tubes in the lower An eddy above and behind the arch tip causes the gas
furnace must be protected against the corrosiveness to recirculate in the superheater tube bank, with a
of the smelt and partially combusted gases. The most reverse gas flow between the superheater and the
widely accepted approach today is to build the furnace upper arch face preventing hot gas from bypassing
and floor of composite tubes (alloy tube material over the superheater surfaces. The angle of the arch is set
a base carbon steel tube). This tube construction to minimize the repose of deposited ash on its surface.
should extend to 3 ft (0.9 m) above the tertiary air
ports. Above this elevation, carbon steel tube and Furnace screen
membrane construction is adequate. In some recovery boilers, the superheater surface
Wide closure plates attached to tubes bent to form is insufficient to adequately cool the combustion gases
air ports and other openings can result in potentially before they enter the boiler bank. This is common in
high localized stress areas. Wide closure plates suffer boilers designed for low steam temperature or when
from corrosion, burn back and cracking. This ad- a recovery boiler’s liquor burning capacity is signifi-
versely affects the air flow area of the port opening cantly increased resulting in an increase in furnace
and has the potential for closure plate cracking that exit gas temperature. A furnace screen can be used
propagates into the furnace wall tubes. The modern to absorb the additional heat, thereby maintaining an
furnace openings are designed without closure plates acceptable temperature of the gas entering the boiler
to minimize this potential (Fig. 17). bank section. When designing a new recovery boiler,
Structural attachments must also minimize tube the required heat absorption can often be accom-
stresses. In high stress areas, a plate stamping is plished through added furnace surface (height) and/
welded to the tubes, and the structural member is or an oversized superheater. Larger furnaces can im-
attached to this plate. This plate stamping is contoured pact the overall building size and therefore increase
to provide additional weld carrying load into the tube the cost of the project. The furnace screen represents
wall, permit flexibility for the absorption of thermally an economical alternative to a larger furnace or su-
induced loads, and lower the potential for fatigue and perheater component.
stress corrosion related failures. The windbox attach- When a furnace screen is required, the screen tubes
ment to the tube wall, shown in Fig. 17, uses plate are in line with the superheater sections to reduce
stampings that are shop-attached, which permits field pluggage potential. The sloped section of the screen
erection without having to make any field attachment originates inside the furnace arch to protect the tubes
welds directly to the pressure part. This design and from falling salt cake deposits and to add strength to
construction philosophy is applied throughout the the sloped tubes. Tubes in the sloped section of the
pressure part enclosure for all attachment welds. screen were originally attached to each other using
round bars on either side of the tubes, welded paral-
Upper furnace and arch arrangement lel to the tubes to provide structural integrity. Current
Combustion is completed in the tertiary zone. The retrofit designs use membrane bar similar to furnace
water-cooled furnace walls and volume above this zone wall construction (see Chapter 23). The top most tube
provide the necessary surface and retention time to cool currently has a half-wide membrane bar on the top

surface to improve structural integrity and further re- amount of the tube circumference available to absorb
duce potential tube damage caused by salt cake falls. heat from the flue gases. This results in fewer super-
heater rows in depth for the same steam temperature
Convection surface rise. Superheater banks can be radiant, convective,
After leaving the furnace, the flue gases pass across or a combination (see Chapter 19). Radiant surface is
the steam-cooled superheater banks to the longflow in front of the furnace arch tip. This surface is the first
boiler bank and finally to the economizer sections. (See steam pass after leaving the steam drum in order to
Fig. 4.) As the gas is cooled, entrained ash becomes utilize non-stainless steel tubing.
less sticky and adheres less to the tube surfaces. As a
result, it is possible to space the tubes in the convec- Boiler bank
tion banks progressively closer together. The closer Today’s kraft recovery boiler generally incorporates
spacing results in higher gas velocities and improved a single steam drum, with a longflow boiler bank ar-
convection heat transfer rates, which in turn permit ranged downstream of the superheater. In passing
a more economical design as less heat transfer surface across the superheater and rear wall screen tubes, the
area is required. flue gas should be cooled below the ash sticky tempera-
ture prior to entering the boiler bank. For ashes with
Superheater extremely low sticky temperatures, particular atten-
The superheater surfaces are exposed to the highest tion must be given to sootblower locations.
gas temperatures and, consequently, are arranged on a The boiler bank is constructed of shop-assembled
12 in. (305 mm) side spacing. This results in very low tube sections arranged as modules inside a water-
gas velocities and prevents the bridging of deposits. cooled enclosure (Fig. 19). Tubes in each section are
In arranging superheater surface, it is desirable to connected to headers, with water entering the lower
maintain low tube temperatures. Lower temperatures header and the steam-water mixture exiting the up-
reduce the potential for high temperature corrosion per headers. As the flue gas enters the bank, it turns
and allow the use of less expensive low alloy steel. downward and flows parallel to the tube length, pro-
Temperatures are reduced by establishing a high viding easy cleanability. Within the bank, a central
steam flow through each tube, by arranging the cavity accommodates fully retractable sootblowers.
coolest steam to flow through the superheater tubes The cavity permits personnel access for visual tube
exposed to the hottest gas temperatures, and by lo- inspection adjacent to sootblower lance entry. Ash
cating the majority of the superheater tube banks deposits dislodged during sootblowing are collected in
behind the furnace arch tip, shielded from furnace
radiation. Superheater surface behind the furnace
arch tip is considered convective surface and does not
experience furnace radiation. Superheater surface
types and arrangements are shown in Fig. 18.
From the drum, saturated steam enters the front
tube row in the first or primary inlet superheater bank ≤0.75 in.
and flows through successive tube loops in parallel (19.05 mm)
with the flue gas flow. (See Fig. 18.) The secondary
superheater is located in the cooler gas region between
the primary banks or behind the primary banks, de-
pending upon final steam temperature. Steam flow in SSH SSH
Boiler
Bank
this secondary superheater is generally opposite to the
gas flow to achieve a higher steam temperature. The
superheater surface, steam direction and bank place-
ment are determined by engineering and balancing PSH1 PSH2
steam temperature and flue gas temperature. Using
these design guidelines for superheater design, ar- Platen
rangement, and materials selection permits final
steam temperatures up to 950F (510C). >0.75 in.
The superheater banks are top supported with the (19.05 mm)
tube elements expanding downward. The tubes are
interconnected with flexible support ties which allow
independent tube expansion. Tube movement is criti-
cal to effective sootblowing. However, lack of tube re-
straints within a bank can lead to failure at the bank’s
top supports.
The superheater can be arranged as pendant sur-
face (clear backspace between tubes) or platen surface
(near-tangent backspace between tubes). Different
heat transfer methods are used when calculating pen- Pendant
dant and platen arrangements. The pendant arrange-
ment has greater effective surface area due to a greater Fig. 18 Superheater arrangements.

retractable sootblowers. Trough hoppers are attached

to the economizer casing to collect dislodged ash deposits.
The economizer surface area is set to achieve a fi-
nal gas outlet temperature approximately 100F (56C)
higher than the feedwater temperature. Although it
is possible to achieve an exit gas temperature closer
to that of the feedwater, the decreased temperature
differential results in substantially increased surface
requirements for small improvements in end tempera-
ture. In addition to this thermodynamic limitation,
concern for cold end corrosion generally establishes a
minimum gas exit temperature around 350F (177C).
The minimum recommended temperature of the feed-
water entering the economizer is 275F (135C) for cor-
rosion protection of the tube surface. With special con-
siderations, the feedwater entering the economizer
can be designed for as low as 250F (121C).
Emergency shutdown system
An emergency shutdown procedure for black liquor
recovery boilers has been adopted by the Black Liquor
Recovery Boiler Advisory Committee (BLRBAC) in the
U.S. An immediate emergency shutdown must be per-
formed whenever water enters the furnace and can
not be stopped immediately, or when there is evidence
of a leak in the furnace setting pressure parts. The
boiler must be drained as rapidly as possible to a level
8 ft (2.4 m) above the mid point of the furnace floor.
Fig. 19 Boiler bank isometric.
An auxiliary fuel explosion can occur when an ac-
cumulated combustible mixture is ignited within the
confined spaces of the furnace and/or the associated
a trough hopper connected to the bank enclosure. Tube boiler passes, duct work and fans which convey the
section inlet headers are widely spaced and vertically combustion gases to the stack. A furnace explosion will
staggered to facilitate ash dropping into the hopper. result from ignition of this accumulation if the quan-
Impact-type particle deposition on the boiler bank tity of the combustion mixture and the proportion of
tubes is less likely to occur with the gas longflow ori- air to fuel are within the explosive limit of the fuel
entation. As a result, the allowable gas velocity in the involved. The magnitude and intensity of the explo-
downflow portion of the bank can be increased. sion will depend upon both the quantity of accumu-
To improve heat transfer, longitudinal fins are lated combustibles and the proportion of air in the
welded to the front and back of each tube. Fins are mixture at the moment of ignition.
tapered at the ends and welded to the tube on both Contacting molten smelt with water can also result
sides. The welds are terminated by wrapping around in a very powerful explosion. The mechanism for a
the end of the fin. This combination of welding tech- smelt-water explosion is keyed to the contact of water
nique and tapered ends assures minimal stress con- with hot liquid smelt. Rapid water vaporization causes
centration at fin termination for fins as large as 1.5 the propagation of a physical detonation or shock wave.
in. (38 mm). In the design and operation of black liquor recov-
ery boilers, every effort is made to exclude water from
Economizer any source from getting to the furnace, or introduc-
The boiler bank surface area is typically set to ing liquor at less than 58% solids. For example, furnace
achieve a nominal exit gas temperature of about 800F attachment details are designed to prevent external tube
(427C). This temperature maintains a reasonable dif- loads, which can lead to stress assisted corrosion.
ferential with the saturated steam temperature [610F
(321C) for a 1650 psig (11.4 MPa) drum pressure] and Recovery boiler auxiliary systems
allows the use of carbon steel casing to enclose the
downstream economizer banks. The modular econo-
mizer has vertical finned tubes arranged in multiple Black liquor evaporation
sections with upward water flow and downward The high black liquor solids concentration required
longflow of gas (Fig. 20). The common arrangement for efficient burning is achieved by evaporating wa-
features two banks. The flue gas enters at the upper ter from the weak black liquor. Large amounts of water
end and discharges at the lower end of each bank. Gas can be economically evaporated by multiple effect
flows down the length of the bank to provide good evaporation. A multiple effect evaporator consists of
cleanability. As in the boiler bank, a central cavity di- a series of evaporator bodies, or effects, operating at
mensioned for personnel access accommodates fully different pressures.5 Typically, low or medium pres-

vessel with the flue gas admitted through a tangential

inlet near the conical bottom. The gas flows in a whirl-
ing helical path to the cylinder’s top and leaves through
a concentric re-entrant outlet. Black liquor is sprayed
across the gas inlet to obtain contact with the gas. The
liquor droplets mix intimately with the high velocity gas
and are centrifugally forced to the cylinder wall. Re-
circulated liquor flowing down the cylinder wall car-
ries the droplets and any dust or fumes from the gas to
the conical bottom, out through the drain, and into an
integral sump tank. Sufficient liquor from the sump
tank is recirculated to the nozzles at the top of the
evaporator to keep the interior wall wet, preventing ash
accumulation or localized drying.
In the cascade evaporator, horizontally spaced tu-
bular elements are supported between two circular side
plates to form a wheel that is partially submerged in
a liquor pool contained in the lower evaporator hous-
ing. The wetted tubes are slowly rotated into the gas
stream. As the tubes rise above the liquor bath, the
surface coated with black liquor contacts the gas
stream flowing through the wheel.
Black liquor oxidation
When a direct contact evaporator is used, odor can
be reduced by oxidation of sulfur compounds in the
liquor before introduction to the evaporator. The oxi-
dation stabilizes the sulfide compounds to preclude
their reaction with flue gas in the evaporator and the
consequent release of reduced sulfur gases. Oxidation
can effectively reduce, but does not eliminate, dis-
charge of these reduced sulfur gases. The direct con-
tact evaporator is the prime source of odor.
Odor is generated in direct contact evaporators
Fig. 20 Economizer isometric. when the hot combustion gases strip hydrogen sulfide
gas from the black liquor:
sure steam is utilized in the first evaporator effect and
then the vapor from one body becomes the steam sup- 2NaHS + CO2 + H2O = Na 2 CO3 + 2H2 S (11)
ply to the next, operating at a lower pressure. Mod-
ern evaporator systems integrate a concentrator into
the flow sequence to achieve the final liquor concen-
tration. As a general rule, each pound of water evapo-
rated from the weak liquor results in one additional
pound of high pressure steam generation in the re-
covery boiler.
For many years, direct contact evaporation was the
technology used to achieve firing solids to the recov-
ery boiler, and may still be necessary to evaporate li-
quor from some special fiber sources. In the direct con-
tact evaporator, liquor and flue gas are brought to-
gether, heat is transferred from flue gases to the li-
quor, and mass transfer of liquor water vapor to the
gas occurs across the liquor-gas interface. Adequate
liquor surface must be provided for the heat and mass
transfer. The gas contact acidifies the liquor by ab-
sorbing CO2 and SO2, which decreases the solubility
of the dissolved solids and requires continuous agita-
tion. The acidification also results in the release of mal-
odorous compounds into the flue gas, a negative as-
pect of direct contact evaporation.
There are two types of direct contact evaporators
used in the recovery unit, cyclone and cascade. The
cyclone evaporator (Fig. 21) is a vertical, cylindrical Fig. 21 Cyclone evaporator.

Oxidation stabilizes the black liquor sulfur by con- liquor temperature is established by controlling the
verting it to thiosulfate: flash tank operating pressure.
There are two designs of liquor burners, the oscil-
2NaHS + 2O2 = Na 2 S2 O3 + H2O (12) lator and the limited vertical sweep (LVS). Oscillators
are generally applied to liquors of lower heating val-
Black liquor oxidation involves high capital and op- ues or percent solids where longer droplet drying time
erating costs; the oxidation step also robs the liquor of is necessary. LVS burners are best used for higher
heating value. Modern recovery facilities incorporate percent solids and heating value liquors where in-
multiple effect evaporators, and the low odor design, which flight, suspension drying of the droplets works well.
eliminates the need for a direct contact evaporator. Both types of burners utilize a nozzle splash plate to
produce a sheet spray of coarse droplets.
Black liquor system The oscillator sprays the black liquor on the furnace
Recovery boilers are operated primarily to recover walls, where it is dehydrated and falls to the char bed.
pulping chemicals. This objective is best realized by The oscillator burners, located in the center of the fur-
maintaining steady-state operation. Recovery boilers nace wall between the secondary and tertiary air ports,
are base loaded at a selected black liquor feed flow or are continuously rotated and oscillated, spraying liquor
heat input, in contrast to power boiler applications in a figure eight pattern to cover a wide band of the
where fuel flow is varied in response to demand for walls above the hearth. Oscillators work well on smaller
steam generation. units, or with a wide range of liquor characteristics.
The black liquor solids concentration can vary with With LVS burners (Fig. 22), black liquor is sprayed
the rate that recirculated ash sheds from heat trans- into the furnace for in-flight drying and devolatization
fer surfaces, the rate it is collected in the precipitator, of the combustible gas stream rising from the char bed.
and the rate it is returned to the black liquor stream The objective of the LVS burner is to minimize the li-
system. Considerable fluctuations can occur, depend- quor on the wall. The LVS gun is normally used in a
ing on which surface is being cleaned by sootblowers, fixed position, but can also sweep vertically to burn
the frequency of sootblower operation, and the rap- low solids liquor or those with poor burning charac-
ping sequence of precipitator collection surfaces. The teristics. LVS burners are normally applied to larger
black liquor system design should provide uniform sized, heavier loaded units.
dispersion of the ash into the liquor to minimize the The temperature and pressure of atomized liquor
fluctuation of solids at the burner. This is increasingly directly impact recovery furnace operations. Lower
important as the liquor solids concentration is in- temperature and pressure generally create a larger
creased into the regime where burners are maintained
in a fixed position and liquor drying is in-flight (not
on the walls). A fluctuation in ash flow would change
the solids concentration by several percent, signifi-
cantly impacting the characteristics of the liquor.
A heater is used to adjust the black liquor tempera-
ture to that required for optimum combustion and
minimum liquor droplet entrainment in the gas
stream. The black liquor is typically heated in a tube-
and-shell heat exchanger, using low pressure steam
on the shell side and black liquor on the tube side.
There are two general categories of heater designs that
can be operated with minimum scaling of the heat trans-
fer surface. The first uses a conventional heat ex-
changer with once-through flow of liquor at high ve-
locity in the tubes. The tubes have polished surfaces to
inhibit scale formation. This heat exchanger is satis-
factory for long periods of operation without cleaning.
The second approach is to recirculate liquor through
a standard heat exchanger with stainless steel tube
surface to maintain high velocities that inhibit scale
formation. This approach also permits long periods of
operation without cleaning.
As the liquor solids concentration increases above
70%, storage can become a problem. Moreover, it be-
comes increasingly difficult to blend recycled ash into
the highly concentrated liquor. Recycled ash can be
returned to an intermediate concentration liquor
stream (of about 65% concentration) prior to final
evaporation in a concentrator. In this type of arrange-
ment, liquor is routed to the recovery furnace from an
evaporator system product flash tank. The as-fired Fig. 22 Limited vertical sweep burner.

particle or droplet of atomized liquor. This minimizes

the entrainment of liquor in the combustion gases
passing to the heat absorbing surfaces. Where wall
drying is carried out, large liquor droplets maximize
the liquor sprayed on the wall and minimize in-flight
drying. For oscillator firing, liquor at approximately
230F (110C) and 30 psig (207 kPa) generally provides
the most satisfactory operation. For LVS burners, li-
quor with a slightly lower pressure of 25 psig (172 kPa)
and higher temperature of 250F (121C) provides ac-
ceptable results.
As the liquor sprayed on the walls builds, it even-
tually falls to the char hearth. The majority of the char
falling from the wall is deposited in front of the pri-
mary air ports, requiring 30 to 50% of the total air to
be introduced through the primary ports.
In-flight drying deposits a minimum of char in the
primary air zone around the periphery of the unit, as
all the drying and a majority of the devolatization are Fig. 23 Dry ash system.
in-flight over the furnace area. Consequently, less
primary air flow is required to keep the char from in
front of the primary air ports. Because the higher li- mix tanks, one serving the boiler and economizer hop-
quor solids concentration dictated by in-flight drying per ash system and one dedicated to the precipitator.
translates into less water evaporated in the furnace, As discussed previously, successful reductions of
a greater fraction of the combustion heat released is chloride and potassium levels in the ash and black li-
available to maintain bed temperatures. Less primary quor have been achieved through precipitator ash
air is therefore required when burning liquor in-flight purging. Ash can be removed periodically to maintain
in contrast to the lower concentration liquors encoun- chloride or potassium concentrations at a specified
tered in oscillator burner applications. level. An ash chute with a rotary valve is added to the
back end of an existing precipitator ash transfer con-
Ash system veyer. When ash purging is desired, the ash conveyer
The sodium compounds entrained in the flue gas is reversed and the ash falls through the chute into a
originate from fume generation and liquor droplet sluice tank.
carryover from the lower furnace. The resultant ash In a wet ash removal system, black liquor is circu-
drops out of the flue gas stream and is collected in lated through the hoppers to sluice the collected ash.
trough hoppers located below the boiler and econo- The sluice discharges directly from the hoppers
mizer modules. The electrostatic precipitator removes through large pipes to the mix tank. However, these
nearly all the remaining ash. pipes can become plugged with ash and overflow li-
The majority of the entrained ash is Na2SO4, and is quor which create safety and cleanliness problems.
commonly referred to as salt cake ash, or simply, salt This has led to wider acceptance of the dry ash me-
cake. The ash collected in the trough hoppers and chanical conveyor system. However, the mechanical
precipitator must be returned to the black liquor to conveyors generally require more maintenance than
recover its significant sodium and sulfur contents. This the wet ash sluice designs.
is accomplished by mixing the ash into the liquor in a The mix tank (Fig. 24) includes a mechanically
specially designed tank. The salt cake ash is trans- scraped screen to assure that all material which passes
ferred to the mix tank through a wet ash sluice sys- to the fuel pumps is small enough to readily pass
tem or a drag chain ash conveyor system. through the burner nozzles. Scraping is provided by
With a dry ash system (Fig. 23), mechanical drag flights on a low horsepower, slow moving agitator. The
chain conveyors are bolted to the bottom of the boiler tank is designed to receive salt cake from the gener-
and economizer trough hoppers, which extend across ating bank, economizer or precipitator hoppers, mix-
the full unit width. The drag chain conveyors are ing it with the incoming black liquor.
equipped with heat treated, high alloy forged link
chains to support and convey the flights. The convey- Combustion air system
ors discharge through rotary seal valves into a collec- B&W’s advanced air management system provides
tion conveyor. The collection conveyor discharges to combustion air at three, and sometimes four, eleva-
the mix tank where the ash is uniformly mixed with tions of the furnace: primary, secondary, tertiary, and
the liquor. potentially quaternary (Fig. 25). The use of at least
Drag chain conveyors are also provided across the three levels allows performance optimization of the
floor of the electrostatic precipitator, beneath the col- respective furnace zones – the lower furnace reduc-
lecting surfaces. The conveyors discharge to mechani- ing zone, the intermediate liquor drying zone, and the
cal combining conveyors, which in turn discharge the upper furnace burnout or combustion completion zone.
salt cake ash through rotary valves into the mix tank. A quaternary air level may also be applied above the
Frequently, the dry ash system is arranged with two tertiary zone for additional NOx or particulate control.

to dry liquor and control bed height, and decreases as

the black liquor solids concentration increases.
The balance of the air is admitted at ambient tem-
perature through the tertiary air ports located above
the liquor guns, and through quaternary ports, if sup-
plied. A velocity damper is again used on each port.
The tertiary (and quaternary) flow increases propor-
tionately as the solids increase.
The secondary air ports are normally arranged on the
longest furnace wall, generally the side walls, as the
furnace is deeper than it is wide. In contrast, the ter-
tiary air ports are arranged on the front and rear walls.
Buildup of smelt and char that restricts the air port
openings can cause a performance deterioration. A
reduction in port area affects air pressure at the port
or air flow through the port, depending on which is
being controlled. When air flow is controlled, the ef-
fect of plugged ports is to increase air pressure and
push the bed farther from the wall. If pressure is con-
trolled, the effect is a resultant decrease in air flow.
This results in less effective burning of the primary
zone with a decrease in furnace temperature and in-
creased emissions.
Primary air port openings are generally cleaned
Fig. 24 Salt cake mix tank. (rodded) every two hours to maintain proper air dis-
tribution and bed height. Automatic port rodders pro-
vide continuous cleaning to maintain a constant flow
The primary air flow quantity must be sufficient to area. The automatic port rodding system stabilizes
produce stable combustion and to provide the hot re- lower furnace combustion for maximum thermal effi-
ducing zone for the molten smelt. Increasing primary ciency and is vital in achieving low emissions.
air flow beyond the level required to achieve these Secondary and tertiary air ports also require peri-
objectives increases the amount of Na2S re-oxidized odic rodding, although the plugging that occurs at
to Na2SO4. The balance of the air at or less than the these ports is generally less severe than at the primary
stoichiometric requirement is introduced above the air ports. In the secondary and tertiary ports, the
char bed at the secondary level to control the rate at rodding equipment can be integrated with the veloc-
which the liquor dries and the volatiles combust, and ity control damper. This is necessary to provide syn-
to minimize the formation of NOx. The additional air chronization of the damper and rodder drives.
required to complete combustion is introduced at the
tertiary level (and quaternary if supplied).
The air system may be arranged as a single-fan, two-
fan (one primary and one secondary/tertiary/quater-
nary) or three-fan system. On larger systems, additional
provisions are made to bias the air flow between respec-
tive air levels, from side to side on the primary and sec-
ondary air, or from front to rear on the tertiary air. This
Carbon Burnout,
gives additional flexibility to the operator. NO / Particulate
The primary air ports are arranged on all four fur- Reduction
nace walls about 3 ft (0.9 m) above the floor. Air is
introduced at a low velocity and 3 to 4 in. wg (0.75 to
1.0 kPa) static pressure which prevents it from pen- Quaternary
Air (0-10%)
etrating the bed. The air lifts the carbon char in front
of the port back onto the bed and maintains ignition.
Tertiary Air
Approximately 40% of the total air is admitted at Liquor (10-20%)
Firing
the secondary zone. The air is introduced at the pres- Equipment
sure and velocity needed to penetrate the furnace 4
Devolatilization
to 6 ft (1.2 to 1.8 m) above the primary air ports. A and Drying Zone
velocity damper is used on each port. Chemical
Proper secondary air mixing with the gases rising Reduction Zone
(Maximum
Secondary Air
( 40%)
from the char bed results in volatile combustion gener- Na So Na S)
ating the heat required for in-flight liquor drying. This Primary Air
( 40%)
secondary zone typically exhibits the highest tempera-
tures in the recovery furnace. The quantity of second-
ary air is dictated by the amount of burning required Fig. 25 Advanced air management system.

To further enhance stability in the lower furnace, pressure during startup, sustain ignition while build-
the primary and secondary air is preheated in a steam ing a char bed, stabilize the furnace during upset con-
coil air heater. Low pressure steam, normally 50 to 60 ditions, carry load while operating as a power boiler,
psig (345 to 414 kPa) is used for preheating. Addi- and burn out the char bed when shutting down.
tional preheating is provided by steam at 150 to 165 In some installations, the recovery boiler must be
psig (1034 to 1138 kPa), typically achieving a 300F able to generate full load steam flow and temperature
(149C) combustion air temperature. When burning on auxiliary fuel. These applications typically arise in
liquors with a low heating value or from a nonwood mills that cogenerate electricity and/or have limited
fiber, air should be preheated to about 400F (204C). power boiler steam generating capability. Increased
Water coil air heaters, sometimes used within the auxiliary fuel capacity can be accommodated by add-
feedwater circuit around the economizer, may also be ing auxiliary burners above the secondary air level
used to provide these air temperatures. (typically at or above the tertiary air level).
Upper level burners allow combination black liquor
Flue gas system and auxiliary fuel firing with minimal interference
Combustion gas exiting the economizer is routed with lower furnace operations. This is not possible
through flues to the electrostatic precipitator and in- when operating the secondary level auxiliary burn-
duced draft fan before discharge through a stack to ers. Also, the upper level burners can provide higher
the atmosphere. steam temperatures at lower loads during startup,
The induced draft fan speed controls the pressure which can be important in mills operating high steam
inside the furnace. The fan is normally located after temperature turbine-generators.
the precipitator, allowing the fan to operate in the The auxiliary fuel burners are in a very hostile
cleaner gas. environment that compromises burner reliability and
A two-chamber precipitator is normally used. Each increases burner maintenance. B&W has always uti-
chamber is equipped with isolation gates or dampers lized rectangular shaped bent tube openings for burn-
and a dedicated induced draft fan discharging to a ers to reduce accumulations of salt cake in the burner
common stack. Flue gas exiting the economizer is di- windbox and to keep the damaging furnace radiant
vided into two flues, which route the gases to the heat away from vulnerable burner and lighter compo-
precipitator’s two chambers. Each chamber typically has nents. The oil atomizer or gas pipe elements are manu-
sufficient capacity to operate the recovery boiler at 70% ally retracted when not in use. They would then be
load, corresponding to a stable black liquor firing mode. manually inserted when needed to start the burners.
When designing the precipitator chamber, the expected The LM2100 auxiliary burner (Fig. 26) is designed
gas flow rate should include that of the sootblower steam to retract the burner and lighter elements into the
and the increased excess air under which the boiler windbox and insert them again to the same location
would operate at a reduced rating. The maximum per- using locally activated air cylinders. In addition to
missible particulate discharge rate then establishes the protection from radiant heat, the use of air cylinders
electrostatic precipitator size. also keeps the fuel elements at the correct position
when inserted. The LM2100 improves burner reliabil-
Cleaning system ity and maintenance. The LM2100 is standard design
Ash entrainment in furnace gases is affected by gas for new recovery boilers and can be retrofit to exist-
velocity, air distribution and liquor properties. The ing recovery boilers of any manufacturer.
design of all recovery unit heating surfaces should
include sootblowers using steam as the cleaning me- Non-condensable gases/waste streams
dium. Gas temperatures must be calculated to make Within the typical pulp and paper mill, there are
certain that velocities and tube spacings are compat- numerous liquid and gaseous waste streams that are
ible with the sootblowers. subject to stringent environmental disposal regula-
High levels of chloride and potassium in the black tions. These waste streams are commonly incinerated
liquor may require greater cleaning frequency. As unit on site. One simple and effective incineration method
overload is increased, additional entrainment of ash is to introduce these streams into an operating boiler.
and sublimated sodium compounds also leads to more Gaseous streams are typically characterized as non-
frequent water washing. This term describes an off- condensable gas (NCG) or stripper off gas (SOG). NCG
line cleaning procedure which uses high pressure is a mixture of sulfur compounds and hydrocarbons
water to eliminate excessive deposits or buildups on mixed with air and is either dilute (DNCG) or concen-
the boiler’s convection surfaces. In addition to excess trated (CNCG). These terms refer to the concentration
quantities of flue gas ash, velocities and temperatures of active compounds within the NCG. If the percent-
throughout the unit are increased, making ash depos- age of sulfur compounds and hydrocarbons is below
its more difficult to remove. the lower explosion limit (LEL) in air, the NCG is con-
sidered dilute, is essentially foul air, and is relatively
Auxiliary fuel system easy to handle. It does, however, present minor chal-
The primary objective of the recovery boiler is to lenges. It can be corrosive and is unpleasant to smell.
process black liquor. However, the unit can fire aux- If the percentage of active compounds is above the up-
iliary fuel, usually natural gas and/or fuel oil. This fuel per explosion limit (UEL) in air, the NCG is considered
is fired through specially designed burners, arranged concentrated. CNCG should be treated as a corrosive fuel
at the secondary air level. These burners raise steam stream. These streams require added precautions.

required to meet more stringent regulations. Recov-

ery boilers can have the ability to capture the SO2 from
NCG combustion. Significant caution and special sys-
tem design are necessary to safely burn NCG in a re-
covery boiler.
DNCGs can often be mixed with the combustion air
for the tertiary air port level on a recovery boiler, or
for the stoker on a power boiler. The primary concern
is to assure adequate main fuel, usually equal to or
above 50% of load, to assure burnout of the gases. To
avoid odor problems, the ducts, windboxes and other
air transport components must be air tight. Corrosion
in the feed ducts can be reduced by mixing the gases
with hot air or heating the mixture. For power boil-
ers, if the sulfur input is high, boiler exit corrosion and
emissions can increase. The corrosion rate can be re-
duced by upgrading alloys and/or coatings or by increas-
Fig. 26 B&W’s LM2100® burner. ing the gas temperature to stay above the dew point.
For CNCG gases, transport must avoid air leakage
that could move the mixture into the explosive range.
The explosion limits for some representative gases Typically, these gases are fired with a support com-
found in NCG are shown in Table 4. The generally bustion source, such as an igniter in close proximity,
accepted LEL for mixtures of gases in air is 2% by to assure burnout. Stainless steel piping is used to
volume, and the generally accepted UEL is 50%. SOG avoid corrosion. One stream explicitly excluded from
is usually a mixture of methanol in air, and is typi- any boiler incineration consideration is terpenes (tur-
cally handled like CNCG. pentine vapor). The UEL of these streams is not de-
These gases require special safety precautions for fined, and terpenes have been the most prevalent
collection and handling. Their escape must be pre- causes of explosions in non-condensable gas collection,
vented in and around the boiler building for person- transport and combustion systems.
nel and equipment protection, and condensate must For either gas, provision must be made to avoid slugs
not be allowed to enter the furnace. For CNCG gases, of liquid entering the furnace. System design uses flame
additional precautions are required to avoid fire and propagation arresters to avoid explosions, and safety
explosion in equipment and transport systems. Posi- interlocks must be integrated into the existing controls.
tive ignition systems are required for gases entering For any type of waste gas, it is important that a
the furnace. complete analysis of the fuel parameters (constituents,
It is generally preferred that these non-condens- amounts, moisture, etc.) be understood so that the
able gases be burned in mill power boilers, as these appropriate systems and safeguards can be designed.
units can more easily include the appropriate safety It is then possible to determine the proper furnace
equipment. One disadvantage to using power boilers temperatures and residence times required to assure
is the requirement to capture the SO2 generated by complete combustion.
combustion of the sulfur compounds, unless the boiler There are also several liquid waste streams with
is equipped with a scrubber. For recovery boilers, the disposal requirements. These include soap, tall oil,
explosion potential due to tube failures does not make methanol, spent acid and secondary sludge. These are
this type of boiler a good application to introduce for- normally blended and combusted with the black liquor
eign streams. BLRBAC does not encourage the intro- fuel. Under specific circumstances, they may be fired
duction of waste streams into recovery boilers. It has, in a separate, dedicated burner. Turpentine, another
however, become more commonplace in recent years liquid stream, is extremely unpredictable and gener-
to utilize recovery boilers for this disposal, as mills are ally restricted from either of the above methods. Han-
dling and combusting recommendations and cautions
can be found in BLRBAC guidelines.
Table 4 Smelt spout system
NCG Gases Explosion Limits
Smelt exits the furnace through specially designed
Lower Explosion Upper Explosion openings at the low point of the floor and is conveyed
Constituent Limit (LEL) Limit (UEL) to the dissolving tank in a sloped water-cooled trough,
Gas % Volume in Air % Volume in Air or smelt spout (Fig. 27). The spout is bolted to the fur-
nace wall mounting box. Most original spout designs
Turpentine 0.8 Not established had the machined face of the spout positioned against
Methanol 7.3 36.0 the outside of the furnace wall tubes surrounding the
Hydrogen Sulfide 4.3 45.0
Methyl Mercaptain 3.9 21.8
opening. While many of this arrangement are still in
Dimethyl Sulfide 2.2 19.7 operation, the fully insertable spout has become com-
Dimethyl Disulfide 1.1 16.1 mon. This type of spout inserts directly into the spout
opening, where the spout taps the smelt directly from

steam shatter jets are located above the smelt stream

to disperse the flow into the tank.
The smelt spout discharge is enclosed by a hood
(Fig. 27). The steam shatter jets are mounted on the
top of the hood, with the nozzle angle adjusted to di-
rect the jet at the smelt stream cascading off the spout
end. The periphery of the hood is equipped with wash
headers to flush the hood walls and prevent smelt
buildup. A door is provided in the hood for operator
access to inspect and to rod the spout and opening.
The dissolving tank is of heavy construction and is
equipped for agitation. One or more agitators, either
side or top entering, are generally used, including an
emergency backup system, such as steam nozzles. A
stainless steel band is commonly used in the carbon steel
tank at the liquor level for corrosion protection, while the
floor is protected with steel grating or poured refractory.
As the smelt is cooled and dissolved into the green
liquor, large quantities of steam are released. The
steam vapors are pulled through an oversized atmo-
spheric vent on the tank to quickly relieve pressure
in the event of a surge or explosion. Smelt particles
and green liquor droplets are entrained in the steam-
air mixture vented from the tank. These vented gases
Fig. 27 Integral smelt spout hood with shatter jet assembly. also contain H2S that must be removed prior to dis-
charge to the atmosphere. Typically, a vent stack scrub-
ber (Fig. 29) is used to reduce H2S emissions and to
the furnace and no smelt contacts the spout opening trap entrained particulates. Weak wash is used as the
tube surface. This has helped alleviate significant scrubbing medium to take advantage of its residual
spout opening wear and deterioration. NaOH, which absorbs the malodorous gases.
Insertable spouts use a round-shaped trough. For
noninserted spouts, the trough is V-shaped to corre-
spond to the V-shaped bottom of the wall opening. Ei- Alternate processes and liquors
ther spout design is constructed of a double wall car-
bon steel trough, with a continuous flow of cooling Soda process
water passing between the inner and outer walls. With few exceptions, the requirements and features
Given the explosive nature of smelt-water reactions of the kraft recovery boiler apply to the soda recovery
and the extreme temperature of the molten smelt, the boiler. Because sulfur is not present in the soda pro-
spout must receive adequate cooling water. A dedi-
cated cooling system with built in redundancy and
multiple sources of backup water assures system reli-
ability (Fig. 28). This system may either be a pressur-
ized cooling system, or more commonly a gravity flow,
induced vacuum system where the water in the smelt
spout is at less than atmospheric pressure. The cool-
ing water is treated in a dedicated, closed cycle to mini-
mize scale-forming contaminants.
Green liquor system
The smelt is dissolved in green liquor in an agitated
tank. Green liquor is withdrawn from the tank at a
controlled density and the volume replaced with weak
wash. The entering smelt stream must be finely dis-
persed, or shattered, to control the smelt-water reac-
tion by rapid dissolution of the smelt into the green
liquor. Excessively large smelt particles entering the
tank can lead to explosions. The outer surface of a large
smelt particle cools quickly as it contacts the green li-
quor, forming an outer shell around its hot core. As
the shrinking forces build, the particle shell explodes,
exposing the hot core to water and resulting in the
sudden release of steam. To eliminate large smelt par-
ticles from reaching the dissolving tank contents, Fig. 28 Smelt spout cooling system.

The liquor is generally characterized by high vis-

cosity and high silica content. The high viscosity lim-
its the level at which liquor can be concentrated in
multiple effect evaporators, and direct contact evapo-
rators are generally required. Higher combustion air
temperatures are used to compensate for the low li-
quor concentrations while allowing flexibility in ad-
justing the firing conditions.
Sulfite process
Pulp produced by the sulfite process is divided into
two broad categories, semi-chemical and chemical.
Semi-chemical pulp requires mechanical fiberizing of
the wood chips after cooking. Chemical pulp is largely
manufactured by the acid sulfite and bisulfite pro-
cesses, which differ from the alkaline processes in that
an acid liquor is used to cook the wood chips. The acid
sulfite process is characterized by an initial cooking li-
quor pH of 1 to 2. The bisulfite process operates with a
pH of 2 to 6. Cooking liquor used in a neutral sulfite
process for manufacture of semi-chemical pulps has an
initial pH of 6 to 10. Spent sulfite liquor, separated from
chemical and semi-chemical pulp and containing the
residual cooking chemicals and dissolved constituents
of the wood, is evaporated and burned, and the chemi-
cals are recovered in a system particular to each base.
Sulfite process pulp mills normally use one of four
basic chemicals for digestion of wood chips to derive a
large spectrum of pulp products: sodium, calcium, mag-
nesium or ammonium. The principal differences in the
sulfite waste liquor of the four bases are the physical
Fig. 29 Vent stack scrubber. properties of the base and the products of combustion.
Sodium This system reconstitutes the base in a form
cess, there is no sulfur reduction in the recovery fur- suitable for reuse in the pulping cycle. The sodium-base
nace. Soda ash (Na2CO3) is added to the recovered green liquor may be burned alone or in combination with
liquor. The ash collected from the boiler hoppers and the black liquor in a kraft recovery unit. The base chemi-
electrostatic precipitator is in the form of Na2CO3 and can cal is recovered as a smelt of Na2S with some Na2CO3
be added directly to the green liquor in the dissolving which would be a suitable makeup chemical for a
tank. A salt cake mix tank is not required. nearby kraft mill. The combination of sulfite liquor and
In the furnace, the soda liquor does not form a suit- kraft liquor, referred to as cross recovery, is common to
ably reactive char for burning in a bed. It is finely pulp mill operations. The proportion of sulfite liquor in
atomized and sprayed into the furnace by multiple cross recovery is generally the equivalent of the sodium
soda liquor burners. The fine spray dehydrates in makeup requirement of the kraft mill cycle.
flight and combustion takes place largely in suspen- Calcium Calcium-base liquor is concentrated and
sion in an oxidizing atmosphere. Combustion air is burned in specially designed furnaces. The furnace and
admitted through primary and secondary air ports boiler design applicable to magnesium-base liquor com-
around the furnace periphery, with the hottest part bustion can also be applied to calcium. This process is
of the furnace just above the hearth. The Na2CO3 col- largely historic today due to its unacceptable effluents.
lects in molten form on the hearth and discharges Magnesium With the magnesium base, a simple
through the smelt spouts. system is available for recovery of heat and total
The Na2CO3 smelt has a higher melting point than chemicals. This is due to the chemical and physical
the kraft process smelt. This makes the soda smelt properties of the base. The spent liquor is burned at
more difficult to tap from the furnace and shatter. elevated temperatures in a controlled oxidizing atmo-
Auxiliary fuel burners can be located low in the side sphere, and the base is recovered in the form of an
walls, close to the spout wall, to keep the smelt hot for active magnesium oxide (MgO) ash. The oxide can be
easier tapping. readily recombined in a simple secondary system with
the SO2 produced in combustion, thereby reconstitut-
Nonwood fiber liquor ing the cooking acid for pulping.
Many countries do not have adequate forest resources Industrial interest in the improved pulp from a vari-
for pulp production. As a result, alternative fiber sources ety of wood species stimulated the development of
are used, such as bamboo, sugar cane bagasse, reeds and pulping techniques using a magnesium base. The two
straw. Black liquor from these fibrous materials requires major pulping procedures, whereby a variety of pulps
special consideration in recovery system design. can be produced, are magnesium acid sulfite and

bisulfite, or magnefite. The basic magnesium recovery sys- BLG, integrated with combined cycle power produc-
tem is appropriate for each of the pulping processes. tion, may offer increased cycle efficiencies and elec-
The heavy liquor is fired with steam-atomizing tricity production.
burners located in opposite furnace walls (see Fig. 30). Process flexibility Gasification technology can re-
The combustion products of the liquor’s sulfur and turn sulfur to the pulping process in a variety of forms
magnesium are discharged from the furnace in the gas (sulfide, elemental sulfur, polysulfide, and/or sulfite).
stream as sulfur dioxide and solid particles of MgO This provides opportunities to produce pulp with sub-
ash. Most of the MgO is removed from the gas stream stantially improved yields and properties.
in a mechanical collector or electrostatic precipitator Availability The fouling of convection pass surfaces
and is then slaked to magnesium hydroxide, or can reduce recovery boiler availability. BLG may pro-
Mg(OH)2. In the complex secondary recovery system, vide a greater availability in that heat transfer sur-
the SO2 is recovered by reaction with the Mg(OH)2 to face fouling in either a power boiler or gas turbine
produce a magnesium bisulfite acid in an absorption heat recovery steam generator might be lower. Inter-
system. This acid is passed through a fortification or mediate cleanup equipment removes sulfur com-
bisulfiting system and is fortified with makeup SO2. pounds and alkali fume from the product gas.
The finished cooking acid is filtered and placed in stor- Safety Smelt-water reactions are largely unpredict-
age for reuse in the digester. able and continue to pose a risk when operating kraft
Ammonium Ammonium-base liquor is the ideal fuel recovery boilers. Low-temperature BLG produces no
for producing a low ash combustion product. Burning molten smelt, eliminating the potential of smelt-wa-
can be accomplished in a simple recovery boiler. The ter reactions, and high-temperature BLG at elevated
ammonia decomposes on burning to nitrogen and pressure is expected to significantly reduce the likeli-
hydrogen, the latter oxidizing to water vapor and thus hood and resultant force of an explosion.
destroying the base. Concentrated ammonium sulfite
liquor is burned in a furnace and recovery system simi-
lar to magnesium-base liquor. SO2 produced in com-
bustion can be absorbed in a secondary system to yield
cooking acid for pulping. The SO2 reacts in an absorp-
tion system with an anhydrous or aqueous ammonium
makeup chemical to produce ammonium bisulfite acid.
In a neutral sulfite semi-chemical plant, the absorp-
tion system produces cooking liquor consisting essen-
tially of ammonium sulfite.
Black liquor gasification

Advanced technologies – gasifier development
A new technology being investigated for the com-
bustion/reduction of black liquor (and thus replacing
the process recovery boiler) is black liquor gasification
(BLG). This technology involves the partial oxidation
of the black liquor to produce a fuel gas that can be
burned in a gas turbine/electric generator or fired in
a power boiler. In the process, sulfur and sodium com-
pounds are recovered from the fuel gas, before it is
sent to the turbine or boiler, for regeneration of the
pulping chemicals.
Potential BLG advantages
The pulp and paper process requires high capital
investment in plant equipment, high internally gen-
erated energy consumption, and high purchased
power consumption. BLG may have the potential to
favorably impact mill energy efficiency, environmen-
tal performance, operating costs and pulp yields.
Energy efficiency The amount of electricity pulp
mills need to import varies considerably from mill to
mill and is dependant on the power/steam cycle used
and on the type of pulp produced. Electrical loads have
increased relative to steam loads as more electricity is
needed to operate recycling, mechanical pulping, and
pollution control equipment. Most mills import a sig-
nificant portion of the mill’s electricity demand, and Fig. 30 MgO recovery boiler.

Emissions BLG processes require that sulfur and fur compounds from the product gas and return them
particulate emissions be removed from the fuel gas. to the pulping process.
As a result, overall emissions from a BLG-based pro-
cess are expected to be low. Status and development needs
Atmospheric pressure BLG has had the most devel-
BLG processes opment to date. Various concepts, both high and low
Black liquor gasification technologies can be clas- temperature, have been in design and pilot stages
sified by operating temperature. Low-temperature since the early 1990s. The first fully commercial pro-
BLG is operated below the first melting temperature cess is an air-blown, high-temperature entrained flow
of the inorganic salts, typically 1112 to 1292F (600 to gasifier with a processing capacity of 15 t/h of dry sol-
700C), to produce a solid inorganic ash. High-tempera- ids. This process provides incremental recovery capac-
ture BLG is operated above the final melting tempera- ity with product gas burned in a boiler.
ture of the inorganic salts, typically 1652 to 1832F (900 High-temperature BLG with combined-cycle power
to 1000C), to produce a molten smelt. Black liquor gas- generation is in development. Various pilot work is
ifiers have utilized either the fluidized-bed (for low-tem- being done for pressurized, oxygen-blown entrained-
perature BLG) or entrained-flow designs (for high-tem- flow reactors and large-scale commercial units are
perature, molten-phase designs), as described in Chap- contemplated for the near future.
ter 18. Typical BLG processes are shown in Fig. 31. Black liquor gasification is a promising technology, but
Low temperature gasifiers operate at 1292F (700C) key issues must be resolved before full commercializa-
or lower so that the organics leave as dry solids. This tion. While current Tomlinson technology is capital in-
type of gasification process is normally conducted at tensive, early BLG installations are expected to be quite
atmospheric pressure and produces a product gas of expensive. Capital costs must be reduced, positive eco-
approximately 200 to 300 Btu/DSCF (11.8 MJ/Nm3 ). nomics must result and the overall economic case must
Minimal gas cleanup is required, and the product gas be strengthened for BLG to provide superior returns.
is generally fired to offset auxiliary fuel in a power Specific gasifier design and process integration issues
boiler. This allows additional black liquor processing exist, including gasifier materials selection, refractory
capacity, provides a useful product gas for auxiliary corrosion, product gas cleanup equipment, tar forma-
fuel use, and is well suited for incremental capacity tion, sulfur removal, and an increased causticizing load.
additions at existing mills. Many activities are underway within the industry to
High temperature gasifiers generally operate at investigate and resolve these and other issues.
1742F (950C) or higher and produce a product gas of An important aspect of the overall process and eco-
approximately 85 to 100 Btu/DSCF (3.9 MJ/Nm3 ) and nomics is the effect of integrating higher yield pulping
a molten smelt of inorganic chemicals. High-tempera- technologies into the BLG cycle (split sulfidity, polysul-
ture BLG can be pressurized and integrated with a fide, etc.), as these can have significant positive im-
combined cycle system for power generation. Product pact on overall economics. They, too, are capital in-
gas cleanup systems are required for the removal/re- tensive and will take some development, but integrat-
duction of sulfur and particulate emissions before the ing them into the process is the key to providing ac-
gas turbine. These systems can also separate the sul- ceptable, positive economic returns.
Steam
Product Gas
to Process or O2
900-1000C Sulfur
Power Boiler Chemicals
600-700C
Black Gasifier Raw
Liquor Black Gasifier
Liquor Gas Gas Gas
Gas Cooling Cleanup
Cooling / Heat Green
Recovery Liquor Clean Fuel Gas
Bed Steam
Solids
Sodium HRSG
Electricity Feedwater
Particulate / Gas H 2S Sulfide
Cleanup Absorber
Green Gas Turbine Flue

Liquor Gas
Low-Temperature, Atmospheric High-Temperature, Pressurized

Black Liquor Gasification Combined Cycle Black Liquor Gasification6
Fig. 31 Black liquor gasification processes.

References
1. Adapted from Hough, G.W., “Chemical Recovery in the 4. Tran, H.N., “Kraft Recovery Boiler Plugging and Pre-
Alkaline Pulping Processes,” Technical Association of the vention,” Notes from the Tappi Kraft Recovery Short
Pulp and Paper Industry, Inc., (TAPPI), p. 197, 1985. Course, pp. 209-218, Orlando, Florida, January, 1992.
2. Adapted from Smook, G.A., Handbook for Pulp and 5. Adapted from Whitney, R.P., Chemical Recovery in Al-
Paper Technologists, Joint Textbook Committee of the Pa- kaline Pulping Processes, TAPPI, Monograph Series No.
per Industry TAPPI/CPPA, p. 69, 1986. 32, p. 40, 1968.
3. Wiggins, D., et al., “Liquor Cycle Chloride Control Re- 6. Taken from Air Products & Chemicals, Inc. presenta-
stores Recovery Boiler Availability,” TAPPI Engineering tion at the American Institute of Chemical Engineers
Conference, Atlanta, Georgia, Sept. 17-21, 2000. (AIChE) Annual Meeting, Miami Beach, Florida, Novem-
ber 15-20, 1998.

Pulp and paper facility.

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The Babcock & Wilcox Company

Major pulping processes

Steam 41 / Chemical and Heat Recovery in the Paper Industry 28-1

Fig. 2 Kraft process diagram.

sodium hydroxide (NaOH) and sodium sulfide (Na2S)

28-2 Steam 41 / Chemical and Heat Recovery in the Paper Industry

Steam 41 / Chemical and Heat Recovery in the Paper Industry 28-3

Boiler thermal performance

28-4 Steam 41 / Chemical and Heat Recovery in the Paper Industry

The portion of the input energy available to generate

Output Input − Losses

Fig. 5 Plant heat balance diagram. (See also Table 2.)

Steam 41 / Chemical and Heat Recovery in the Paper Industry 28-5

The difference between Step 2 and Step 3 is the heat

28-6 Steam 41 / Chemical and Heat Recovery in the Paper Industry

factors result in an increased quantity of theoretical

Steam 41 / Chemical and Heat Recovery in the Paper Industry 28-7

consists of a matrix of carbon and inorganic sodium 350

Sulfur Dioxide (at 8% O ), ppm

28-8 Steam 41 / Chemical and Heat Recovery in the Paper Industry

boiler, particularly if allowed to sinter and harden. Deformation

diate size particles (ISP), a class of particles between

Steam 41 / Chemical and Heat Recovery in the Paper Industry 28-9

28-10 Steam 41 / Chemical and Heat Recovery in the Paper Industry

Carbon Type Incoloy Inconel

Expansion coefficient Alloy 625, 825

Steam 41 / Chemical and Heat Recovery in the Paper Industry 28-11

28-12 Steam 41 / Chemical and Heat Recovery in the Paper Industry

tainer Corporation) in Hodge, Louisiana; it generated

Fig. 14 Carbon steel tube surface protected with GenClad®.

little or no slope, and is intended to maintain a pool of Secondary

Lower furnace floor support design has evolved over Secondary

Steam 41 / Chemical and Heat Recovery in the Paper Industry 28-13

(a) Horizontal (b) Five-Pass Crossflow (c) Longflow (d) Three-Pass

Fig. 16 Recovery boiler economizer arrangements.

28-14 Steam 41 / Chemical and Heat Recovery in the Paper Industry

Steam 41 / Chemical and Heat Recovery in the Paper Industry 28-15

furnace to minimize deposition on convection surfaces.

28-16 Steam 41 / Chemical and Heat Recovery in the Paper Industry

Steam 41 / Chemical and Heat Recovery in the Paper Industry 28-17

retractable sootblowers. Trough hoppers are attached

28-18 Steam 41 / Chemical and Heat Recovery in the Paper Industry

vessel with the flue gas admitted through a tangential

Steam 41 / Chemical and Heat Recovery in the Paper Industry 28-19

28-20 Steam 41 / Chemical and Heat Recovery in the Paper Industry

particle or droplet of atomized liquor. This minimizes

Steam 41 / Chemical and Heat Recovery in the Paper Industry 28-21

to dry liquor and control bed height, and decreases as

28-22 Steam 41 / Chemical and Heat Recovery in the Paper Industry

Steam 41 / Chemical and Heat Recovery in the Paper Industry 28-23

required to meet more stringent regulations. Recov-

28-24 Steam 41 / Chemical and Heat Recovery in the Paper Industry

steam shatter jets are located above the smelt stream

Steam 41 / Chemical and Heat Recovery in the Paper Industry 28-25

The liquor is generally characterized by high vis-

28-26 Steam 41 / Chemical and Heat Recovery in the Paper Industry

Black liquor gasification

Steam 41 / Chemical and Heat Recovery in the Paper Industry 28-27

Green Gas Turbine Flue