Professional Documents
Culture Documents
3-3 Evaporator Fouling
3-3 Evaporator Fouling
3-3 Evaporator Fouling
(~2Na2CO3• Na2SO4 )
eventually reduces the rate of heat transfer and 1.5
Burkeite +
40% of
Na2CO3/Na2SO4 Dicarbonate
evaporation in the effect. These sodium scale deposits are mass ratio in
N. Am.
mills
soluble in water or weak black liquor so they can be black liquor solids 1.0
Na2SO4
0.0
50 55 60 65 70 75
3.3-1
crystallizes, sulfate is removed from solution faster than Slide 7
carbonate, and the dissolved salts remaining become Transition to Dicarbonate Crystallization
richer in carbonate.
To control sodium salt scales in black liquor evaporators, • Crystallization removes dissolved Na salts from BL
we must know whether burkeite, dicarbonate, or both are • If burkeite first, two Na2SO4 removed per Na2CO3
crystallizing. Recent data from 29 different kraft pulp
mills indicate that, in 40% of these mills, burkeite or a • When Na2SO4 depleted, burkeite can’t form
mixture of burkeite and dicarbonate crystallize first as the • Solids content at onset decreases with increasing
liquor is concentrated, but dicarbonate may eventually be CO3 / SO4 ratio in black liquor
crystallized. In the other 60% of the mills, dicarbonate
crystallizes first.
• Crystallization point 1-5% above critical solids • Reduce total Na in black liquor
– Control AA-to-wood target at digester
• First salt depends on CO3 / SO4 ratio in BL – Reduce NaCl deadload
– Low ratios: Burkeite (~2Na2SO4•Na2CO3) • Operate about 2 - 3% below critical solids
– High ratios: Dicarbonate (~2Na2CO3•Na2SO4)
• For BL > 110°C (230oF), slight inverse
solubility of salts The situation in black liquor concentrators is slightly
different. All concentrators operate well above the critical
solids so sodium compounds are always going to
The total sodium content in black liquor is typically near crystallize as water is evaporated from black liquor. The
20%, and Na2SO4 is frequently between 3 and 6 wt% of approaches to avoiding scaling are (a) to encourage the
BLS, so the critical solids is usually between 50% and sodium salts to crystallize on the suspended crystals
55% black liquor dry solids. instead of on the heat transfer surfaces, and (b) to avoid
massive nucleation events that produce very fine crystals
Slide 7 summarizes the factors that control when the that agglomerate on heat transfer surfaces.
transition from burkeite to dicarbonate crystallization
occurs. This transition is more difficult to predict, and Falling-film evaporators and concentrators are not
advanced calculation methods are required [for example particularly susceptible to burkeite fouling, but are to
see reference 2]. dicarbonate fouling. Slide 9 shows the characteristics of
sodium salt scales in these units.
3.3-2
Soluble Na Scale in FF Evaporators Slide 9 Evaporator Configuration Where Slide 11
and Concentrators Dicarbonate Fouling Will Occur in 1B, Why?
• Falling film evaporators are not susceptible to
burkeite scale No Crystals Burkeite Dicarbonate
A situation expected to suffer from dicarbonate scaling is This improved mode of operation is illustrated in Slide 12.
illustrated in Slide 11.
3.3-3
Slide 13
Raising Product Solids Avoids DicarbonateSlide 12 Insoluble Calcium (Ca) Scale
Fouling in 1B, Why? What about 1A?
Concentrator design plays a major role in avoiding Na • Difficult to control Ca input to black liquor
scaling, but there are two steps that can be taken with – Good debarking helps
existing concentrators that help: ensure that liquor
distribution is uniform, and start up the concentrator on
stored product liquor that contains the same sodium salt Slide 15 describes the mechanism by which calcium in
crystals that will be produced during evaporation. black liquor is converted to scale.
Accumulation of flakes of scale and fiber can cause poor
liquor distribution and increased Na scaling. Fiber control Slide 16 shows a schematic diagram of the calcium
will be discussed later in this section. deposition mechanism. Calcium is released when the
organics break down at higher temperatures [3]. It
Slide 13 describes insoluble calcium scales. Calcium scale precipitates as either CaCO3 or pirssonite. Both are very
in evaporators is usually CaCO3, which is nearly insoluble insoluble and form insoluble deposits on the heat transfer
in water or alkaline solutions. At higher dry solids levels, surfaces of evaporators.
where the sodium salts are more concentrated, CaCO3 can
co-precipitate with Na2CO3 as the double salt, pirssonite.
Pirssonite is partially soluble in water, so calcium deposits
are often not as severe a problem in concentrators as in
evaporators.
3.3-4
Slide 15 Slide 17
Mechanism For Ca Precipitation Reducing Ca Scale in Evaporators
3.3-5
Slide 20 presents information on fouling due to black Slide 22
liquor soap. Soap by itself does not precipitate as a Fiber Fouling in Falling Film Units
deposit, but can be incorporated in soluble and insoluble
scales and contribute to fouling. Soap also contains higher
concentrations of both dissolved calcium and fiber than • Clumps stick in distributor plate openings
the rest of the black liquor, so it can contribute to
insoluble Ca scaling and to fouling due to fiber. The only • Causes poor liquor distribution
remedy is better soap removal. • Only remedy is fiber removal from liquor
Slide 20
• Install and maintain fiber filter
Fouling Due to BL Soap – Target < 100 ppm fiber in BL streams to evaps
Slide 21
Fouling Due to Fiber Plugs • Lignin precipitates at low liquor pH
– Deposit samples are soft and gunky
3.3-6
Slide 24 During a boil out the dilute boil-out liquor is transferred to
Cleaning Evaporators a spill or boil-out tank and then typically pumped back to
the weak liquor system that feeds the evaporator. Because
• Boiling out it contains dissolved scale and deposits, the boil-out liquor
– Dissolves Na scales is richer in Na+, CO3=, and other scale species, than the
– Removes hard scales by thermal shock normal feed liquor [6]. It is important to transfer this
• Hydroblasting
waste stream back to the evaporator feed as slowly as
possible to avoid recurrent massive nucleation and rapid
• Chemical cleaning fouling events, as shown in Slide 27.
– Muriatic acid
– Sulfamic acid Slide 27
Boil Out Problems: Rapid Recovery
– Chemical / chelant wash
1 2 3 4 5 6
Slide 25
Boiling Out Evaporators
– Back half
Shortcut procedures are often employed for evaporator
• Wash liquid
boils to increase time on line for the equipment. Slide 28
– Weak liquor (15% to 35%)
presents mill data for a series of rapid boils in a falling
– Condensate film evaporator operating at about 65% total solids
– Fresh water content. The minimum solids reached rarely drops below
the critical solids content of ~53% and the duration of the
boil is insufficient to dissolve any soluble scale deposits.
In this situation it would be better to wash for longer once
For a full boil out, combined condensate, weak liquor, or per day than follow a shortcut procedure each shift.
water can be used. During the boil out the evaporators are
not working at full capacity, and the boil out results in Boil Out Problems: Shortcut Boils Slide 28
additional water that must be evaporated. An approach to What is wrong with this picture?
reducing the impact of boiling out on overall evaporator 70
throughput is to boil out only the portion of the set that is 68
fouled. One such arrangement is shown in Slide 26. 66
64
Total Solids, wt. %
Slide 26 62
Front Half Boil Out 60
58
56
1 2 3 4 5 6 54
Solubility Limit
52
50
12/17/04 12/17/04 12/18/04 12/18/04 12/19/04 12/19/04 12/20/04
0:00 12:00 0:00 12:00 0:00 12:00 0:00
3.3-7
Slide 29 Slide 31
Boil Out Guidelines Implications for Evaporator Operation
SUMMARY
ACKNOWLEDGEMENT
Due to the variety of mechanisms for scaling and fouling
of evaporators, they work best when they are operated in a Appreciation is expressed to Christopher L. Verrill,
steady manner. Steady feed and steady transfer of liquor International Paper, author of the 2007 manuscript, which
between the effects allows them to avoid some of the was the starting point for this 2008 revision.
conditions that promote rapid surface fouling. The most
effective ways to mitigate recurrent soluble scale fouling FURTHER READING
can be counter-intuitive, e.g., higher product solids is
better, and less frequent washing is better. It may be 1. Frederick, W. J. Jr., Shi, B., Euhus, D. D., and
difficult to overcome operating culture to implement such Rousseau, R. W., Crystallization and Control of
strategies; therefore, hard piping changes or automated Sodium Salt Scales in Black Liquor Concentrators,
procedures are sometimes the only way to solve these Tappi J. 3(6):7-13 (2004).
problems. More information on evaporator operation and
fouling can be found in references 7 and 8. 2. Soemardji, A. P., Verrill, C. L., Frederick, W. J. Jr.,
and Theliander, H., Prediction of Crystal Species
Slides 30 and 31 summarize the implications of black Transition in Aqueous Solutions of Na2CO3 and
liquor fouling on evaporator operation. Na2SO4 and Kraft Black Liquor, Tappi J. 3(11):27-32
(2004).
3. Frederick, W. J. Jr., and Grace, T. M., Preventing
Slide 30
Calcium Carbonate Scaling in Black Liquor
Implications for Evaporator Operation Evaporators, Southern Pulp and Paper Mfgr. Part 1,
42(8):22-24 (1979); Part 2, 42(9):21-29 (1979).
• Many potential causes for fouling 4. Lansdell, G. M., Frederick, W. J. Jr., Schmidl, W.,
Euhus, D. D., An Investigation of the Accelerated
• Remedies often involve other areas of the mill CaCO3 Fouling in Evaporators Processing Black
– Recovery boiler for Na2SO4 input to BL Liquor from Displacement Batch Kraft Pulping,
– Recaust for Na2CO3 input to BL TAPPI Pulping Conf., Session 59, Boston (November
– Digester for total Na and residual EA 5-8, 2000).
– Brownstock washing / screening fiber input to BL 5. Ulmgren, P., The Removal of Aluminum from the
– Wood room for bark (Ca) and dirt input to liquor Recovery System of a Closed Kraft Pulp Mill, Proc.
1985 Int. Chemical Recovery Conf., Tappi Press,
Atlanta, pp. 299-303 (1998).
6. Verrill, C. L., DeMartini, N. A., Evaporator Boilout
Guidelines, Paper 37-1 at TAPPI Engineering,
Pulping, and Environmental Conference, Atlanta, GA
(November 6-8, 2006).
3.3-8
7. Grace, T. M., Black Liquor Evaporation, in Pulp and
Paper Manufacture, Volume 5-Alkaline Pulping, Joint
Textbook Committee of the Paper Industry, Atlanta
(1989).
8. Venkatesh, V, and Nguyen, X. N., Evaporation and
Concentration of Black Liquor, in Chemical Recovery
in the Alkaline Pulping Process, Tappi Press, Atlanta
(1992).
3.3-9