AN OVERVIEW OF VARIOUS STRATEGIES FOR BALANCING SALTCAKE, CHLORIDE AND POTASSIUM LEVELS IN AN ECF KRAFT MILL INTRODUCTION A.

Mark Minday Senior Process Engineer Eka Chemicals Marietta, Georgia USA Michael A. Burke Process Engineer Eka Chemicals Marietta, Georgia USA Douglas W. Reid Senior Process Engineer Eka Chemicals Marietta, Georgia USA Craig J. Brown Vice President Eco-Tec Inc. Pickering, Ontario Canada

Presented at the TAPPI Minimum Effluent Symposium, San Fransisco, Oct.23-24, 1997.

ABSTRACT

Mills today are faced with the difficult task of operating costcompetitive facilities, while meeting increasingly stricter environmental regulations and making higher quality products as demanded by market forces. In the U.S., the Environmental Protection Agency (EPA) has proposed joint air and water regulations, known as the Cluster Rule (1). These regulations will encourage mills to implement technology to reduce effluent pollutant loads (e.g., AOX) at the source. In addition, the proposed EPA Cluster Rule requires the implementation of best management practices (BMPs) to contain pulp and liquor spills. COD limitations are not included in the proposed ruling, but stricter regulation may follow later. If so, further closure of the screen room may be necessary. Thus, the Cluster Rule will require the liquor cycle to be closed to a higher degree than has normally been practiced. As mill closure increases, so does the accumulation of nonprocess elements (NPEs) in the kraft recovery liquor cycle (2). These NPEs, if not properly treated, can cause a number of operational problems. One such problem is caused by the accumulation of chloride (Cl) and potassium (K) in the recovery cycle. Chloride and potassium are alkali-soluble elements that are always present in kraft pulp mill process streams. Under normal operating conditions, chloride enters the mill with the wood, especially sea-borne logs, and to a smaller degree with the water and makeup chemicals used in pulping. On the other hand, potassium primarily enters the system with the wood. Table 1 shows typical values of Cl and K levels in wood, makeup chemicals and makeup water (3). Table 1 . Levels of Cl and K in Wood, Makeup Chemicals and Makeup Water Source Chlorides Conc., ppm 67 15 1,000 5,000 100 & 20 Potassium Conc., ppm

As mill closure increases, so does the accumulation of nonprocess elements in the kraft liquor cycle. The proposed EPA Cluster Rule requires the implementation of best management practices (BMPs) to contain both pulp and liquor spills. This will require the liquor cycle to be closed more than is normally practiced. For the kraft recovery boiler, mill closure causes increased chloride and potassium concentrations in the as-fired liquor, resulting in a lower melting point ash in the boiler. This can lead to accelerated plugging in the upper superheater and boiler bank sections, resulting in downtime for water washing. Two technologies for removing chloride and potassium from precipitator dust are described in detail. One is an evaporator/crystallizer based process, while the other uses ion exchange. The evaporator/crystallizer process is effective for both chloride and potassium removal (90%), whereas the ion exchange process is more efficient at chloride removal (95%) and less selective in removing potassium (5-10%). The latter is more effective at saltcake recovery (95%) compared to the former (80%). The best suited technology depends on the requirements of each mill. Computer simulation was used to model an actual ECF kraft pulp mill. It was used to simulate various degrees of recovery cycle closure for a BMPs case, resulting in a need for chloride and potassium removal. The two chloride and potassium removal technologies were evaluated for this case, showing only 40 to 45% of the total precipitator dust required treatment by either process to prove effective.

Wood Chips Douglas fir White oak Makeup Caustic Makeup Saltcake Makeup Lime Fresh Water (Fiberline Recovery)

657 1,162 700 100 100 2

Typical mill operation would have about 95% of the K load coming from the wood chips and about 70% of the Cl load coming from the wood chips and water. The concentration of Cl and K in the kraft recovery cycle varies from mill to mill, depending on the inputs (4), the degree of mill closure (5) and the liquor sulfidity (6). The range of inputs with wood are 1.2 to 14 kg/adt as chloride and 0.7 to 4 kg/adt as potassium. As mills close up, even moderate inputs of Cl and K becomes increasingly important (7). Mills with increased closure can build the Cl and K levels up to 4 - 12 times greater than mills which operate fairly open (5). Increased chloride and potassium concentrations in the kraft liquor cycle can result in accelerated corrosion, boiler plugging and ring formation in the lime kiln. Boiler plugging is a concern to many mills due to the loss in production, when the recovery boiler is shut down for a water wash.

superheater, generator bank and economizer rather than the lower superheater because the lower superheater temperatures are too high for condensation to occur (3). In the lower superheater, carryover is dominant, forming hard, fused and smelt-like deposits. In the generating bank and economizer region, where the flue gas temperature is low enough, almost all vapors condense to form dust. In this region, carryover is completely solidified and will not stick readily on tube surfaces. Deposits consist of more than 99.8 wt % water soluble compounds, primarily sodium sulfate and sodium carbonate, with small amounts of sodium hydroxide, sodium chloride, potassium salts and reduced sulfur compounds. Carryover, which comes from physically entrained smelt and unburned black liquor particles, has similar composition to the smelt (i.e., 20-30 wt % Na2 SO 4 , 60-70 wt % Na2 CO3). Also, the chloride and potassium content of the carryover has about the same content as found in the smelt. Condensation material originates from vapors that condense to form submicrometersized fume. The fumes high specific surface area makes it very reactive in the oxidizing sulfur-bearing flue gas, converting most of the Na2CO3 to Na2SO4 . Thus, it contains primarily Na2SO4 and is enriched with chloride and potassium salts. There is only a small amount of carbonate present. Condensation deposits contain no reduced sulfur compounds and no hydroxides (9). The rate of formation of deposits on recovery boiler tubes is a function of the amount of liquid phase present in the deposit. The amount of liquid increases with temperature. Below a critical temperature, the first melting temperature, deposits have no liquid and act as solid particles. When the deposits contain between 15% and 70% liquid phase, they will be sticky and cause rapid plugging if not removed. The sticky temperature is the temperature that results in a sticky deposit with 15% liquid phase (TSTK). The temperature corresponding to a deposit with 70% liquid phase is known as the radical deformation temperature (TRD). As the flue gas temperature decreases as it passes through the various tube sections of the boiler, the sticky temperature and the radical deformation temperature define a region in which deposits are expected to be worse (3). Figure 1 shows the effect of Cl on TSTK and TRD for a typical carryover deposit containing 5 mole % K/(Na + K). The sticky temperature zone is bordered by the TSTK curve as a lower limit and the T RD curve as the upper limit. In this zone, deposits are sticky, which increases deposit accumulation. Outside the range, deposits either do not contain enough liquid phase to be sticky or contain so much liquid that they slag and do not build up (9).

BACKGROUND

Recovery Boiler Deposit Formation and Plugging

The presence of 40% to 50% inorganic material in black liquor being fired to a recovery boiler forms a low melting temperature ash or smelt after combustion. The presence of such a large quantity of low melting temperature ash makes this application one of the toughest for industrial steam and power generation. As a result of burning black liquor, fly ash deposits on tube surfaces in the upper furnace. These deposits grow and eventually restrict flue gas flow if they are not occasionally removed from the tube surfaces by sootblowers. Massive deposit accumulation will lower the heat transfer efficiency of the boiler, resulting in poorer quality steam, and could lead to an unscheduled shutdown due to plugging of flue gas passages. Under some conditions, deposits can form a localized corrosive environment, possibly resulting in tube damage. As boilers are pushed to higher liquor loads, there is more fly ash and higher flue gas temperatures leading to more deposit formation (8). Deposits are derived from two different sources (9): (1) Carryover. Smelt and/or partially burned black liquor particles physically entrained in flue gas. (2) Condensation. Fume or dust resulting from the condensation of compounds volatilized from the lower furnace. Condensation occurs either on cooled surfaces or indirectly in the flue gas stream. The composition of carryover and condensation is not the same. Deposits and electrostatic precipitator (ESP) dust are a mixture of both carryover and condensation. Condensation usually forms in the upper 2

Figure 1. The Effect of Chloride on the Sticky Temperature Zone

Figure 2 .

Effect of Chloride and Potassium on Deposit Temperature (TSTK)

Sticky

Chloride has been found to lower both the sticky deposit and the radical deformation temperatures of recovery boiler fireside deposits (7,8,9). The effect of increasing potassium concentrations is similar to chloride, but not as pronounced. Potassium works together with chloride to decrease the sticky deposit temperature and the radical deformation temperature. At low chloride concentrations, potassium has very little effect on sticky deposit temperature. On the other hand, when the chloride mole % [Cl/(Na+K)] exceeds 10%, potassium has a significant effect on lowering the sticky temperature. Refer to Figure 2, which is a plot of Isaaks data as reported by Tran (9). Tran, Barham and Reeve have reported that mills with low chloride in the as-fired black liquor dry solids, less than 1.6 Cl/(Na+K) mole %, or 0.5 wt % chlorides, have an insignificant amount of plugging caused by potassium (7). Here the sticky temperature decreases only slightly, from 740E to 720EC, as the potassium content increases significantly from 4 K/(Na+K) mole % to a high of 15 K/(Na+K) mole %. In the region where the flue gas temperature is higher than 720EC, the Na2S effect on deposit thermal characteristics becomes dominant. Here the effect of Cl and K in deposits is minimal. Thus to reduce plugging, mills should operate the as-fired black liquor dry solids at less than 1.5 Cl/(Na+K) mole %.

Chloride and Potassium Removal

Various methods have been proposed in the past to remove chloride and potassium from the liquor cycle. Of the different methods used or proposed, the common practice is to purge precipitator dust, because it is enriched in both Cl and K. That is, the molar ratio of chloride and potassium in the precipitator dust is greater than in the strong black liquor. Typical enrichment ratios are 2.5 for chloride and 1.5 for potassium, whereas the range for each is 1.5 to 4.0. Chloride has also been removed by evaporating of white liquor to recrystallize sodium chloride (10) and by leaching precipitator dust and disposing of the chloride-rich leach liquor (11). Increasing liquor sulfidity also helps remove chloride from the system. Here high sulfur input to the recovery boiler results in high SO2 concentration in the flue gas. This leads to the formation of HCl vapor, which purges Cl from the system via the recovery boiler stack (6). More recent developments include: electrodialysis using a bipolar membrane (12) and a crystallization process which selectively removes sodium sulfate crystals from a concentrated filtrate stream containing chloride and potassium (13). The crystallization process is currently being used in Champion International Corporations bleach filtrate recycle process in Canton, North Carolina (14). Eka Chemicals has developed a crystallization process, precipitator dust recovery (PDR), which separates sodium sulfate crystals from dissolved electrostatic precipitator (ESP) dust. Chloride and potassium are concentrated in the evaporator/crystallizer, then purged as a filtrate stream after filtration. A portion of this filtrate is purged to maintain the 3

proper Cl and K levels in the recovery cycle. An approach introduced by Eco-Tec Inc., precipitator dust purification (PDP), uses an ion exchange process to selectively remove chloride from the ESP dust. Both processes will be described in detail in the next section. After discussing these, each is evaluated in a WinGems model of an actual ECF kraft mill. These simulations will show the impact increased liquor cycle closure has on chloride and potassium concentrations in the kraft liquor cycle and how either process can effectively lower these high Cl and K concentrations to an acceptable level.

1.00 0.95

Na2 SO 4
0.90 0.85 0.80 0.75 0.70 0.65

K3Na(SO 4)2 NaCl

0.0 0.2 0.4 0.6 0.8 1.0

PROCESSES FOR POTASSIUM REMOVAL

CHLORIDE

AND

0.60 Mole Ratio SO 4 / (SO4 + 2 Cl)

Precipitator Dust Recovery (PDR)

Figure 4. Phase Diagram For Na+ / K + / SO4-2 / Cl - System Dust solution is fed to the crystallizer and water is evaporated, which concentrates all the chemical species in the dust. As the process operates, sodium sulfate begins to crystallize. After solids have accumulated for a period of time, the filter system is started. While sodium sulfate is removed by the filter, chloride and potassium continue to accumulate in the crystallizer liquor. This accumulation is represented by the arrow in Figure 4. When the potassium concentration reaches a target value, the purge is turned on. The composition of the liquor at steady state is represented by the rectangle in Figure 4. If the potassium concentration gets too high, glaserite [K3Na(SO4)2] will crystallize, which is undesirable because it puts potassium back into the recovery loop.
1.00 0.95 0.90
.

Background. The five major components in precipitator dust are sodium, sulfate, carbonate, chloride and potassium. Figure 3 shows the results of precipitator dust analyses from six North American mills. When these species are present in solution, one or more salts may precipitate depending on the relative concentrations of the species. The phase diagram shown in Figure 4 identifies the salt forms which may crystallize from the four-component system sodium / potassium / sulfate / chloride (15). The composition of the precipitator dust and dust solution is represented by the oval in Figure 4.
70 60 50 40 30 20 10 0 Cl K CO3 Component Na SO4

Na2SO 4 2 Na2 SO 4 Na2CO 3

0.85 0.80 0.75 0.70 Mole Ratio Na / (Na + K) 0.65 0.60 0.0 0.2 0.4 0.6 0.8 1.0 Mole Ratio SO 4 / (SO4 + CO 3)

K3 Na(SO4)2 Na2 CO3 H2O

.

Figure 3. Composition Of Precipitator Dust From Six North American Mills

Figure 5. Phase Diagram For Na+ / K + / SO4-2 / CO3-2 System If the precipitator dust contains a significant amount of carbonate (e.g., mill 6 in Figure 3), then a double salt of sodium sulfate and sodium carbonate called burkeite (2Na2SO4Na2CO3) will crystallize. The phase diagram shown in Figure 5 describes the four-component system sodium / potassium / sulfate / carbonate, assuming no chloride is

present (18). Chloride tends to extend the sodium sulfate phase region.

outside the building into the atmosphere. Vacuum pumps may also be used instead of steam ejectors, in which case the aftercooler is not required. Precipitator Dust Recovery Process Performance. When sodium sulfate crystallizes, this process is capable of removing 90% of the chloride and potassium from the incoming dust while recovering 70-80% of the sodium and sulfate (see Table 2). Burkeite formation increases the sodium recovery efficiency, while glaserite formation decreases the potassium removal efficiency. Typical system performance is shown in Table 2. This table is based on treating 100 tpd of ESP dust. Table 3 shows typical ranges for utility usage by this process. Because precipitator dust composition varies widely, the numbers in Table 2 will not be applicable to every case, but the numbers in Table 3 are less dependent on dust composition. Table 2. Material Balance For PDR Process, Ton per 100 tpd of ESP Dust Componen t Sodium Potassium Chloride Sulfate Carbonate * Water Total Flow ESP Dust 32.2 3.2 1.3 59.8 3.5 100 Salt Cake 24.6 0.35 0.1 46.6 5.4 77.1 Chloride Purge 7.6 2.85 1.2 13.2 48.8 73.6 % Removal 23.6% 90% 90% 22% as CO2 -

Burkeite formation represents a dead load of carbonate in the system, but it increases the sodium recovery efficiency. Even when the precipitator dust does not have enough carbonate to crystallize burkeite, which is usually the case, carbonate is detrimental because it shrinks the sodium sulfate phase region, thus reducing the removal and recovery efficiencies of the process. This situation can be avoided by acidifying the dust solution to a pH of 3 to drive off the carbonate as carbon dioxide. Sulfuric acid is usually available at a pulp mill. Acidic saltcake solution from a chlorine dioxide plant may also be used as an acidifying agent, although it will increase the solids loading in the crystallizer and filter.

Precipitator Dust Recovery Process Description. The following is a brief description of this process to provide an overview of the process equipment and operation. Please refer to the schematic diagram in Figure 6. Precipitator dust is transported to the dissolving tank and dissolved in hot water to form a solution that is approximately 30% dissolved solids. The hot water is recycled condensate from the vacuum system (described later). The cone bottom prevents solids from settling to the bottom of the tank. The dust solution pump acts as an agitator and pumps dust solution to the crystallizer. The crystallizer operates at about 70 C and 250 mmHg (abs), with vacuum being pulled by a steam ejector. The crystallizer serves three purposes: Evaporate water from the dust solution. Crystallize sodium sulfate from the dust solution. Concentrate all other chemical species in the liquor.

* Sulfuric acid as 5.72 ton/100 ton ESP dust is required to remove carbonate as CO2. An additional amount of Na2SO4 is produced, 8.3 ton/100 ton ESP dust. Neither was added to table. Table 3. Typical Process Utility Usage UTILITY Makeup Water Cooling Water LP Steam** HP Steam* USAGE PER MTPD DUST less than 0.5 l/min 40 - 60 l/min 75 - 100 kg/hr 450 - 900 kg/hr (total)

A circulation pump circulates slurry through the reboiler and back into the crystallizer. Low-pressure steam fed to the reboiler evaporates the water from the dust solution and maintains the level in the crystallizer. The filter feed pump supplies slurry from the crystallizer to the sulfate filter, which is a bottom-feed rotary drum vacuum filter. The filter vacuum is maintained by a steam ejector at about 500 mmHg (abs). The filter removes saltcake from the system and discharges it into the sulfate recovery tank, where it mixes with strong black liquor and is pumped to the recovery area. A portion of the filtrate is purged from the process and the remainder returns to the crystallizer. Water vapor from the crystallizer and steam from the discharge of the ejectors are condensed in two heat exchangers and collected in the hot water tank. Noncondensibles discharge 5

* This is independent of tonnage. ** Based on a stand alone system. May be significantly reduced by incorporating PDR in evaporator steam circuit.