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Abstract
The reduction of mill effluent discharge as a result of stringent environmental legislations can
have a significant impact on sodium (Na) and sulfur (S) balances in the kraft pulping process. In
order to maintain a proper balance of Na and S, kraft mills may need to adopt different makeup
strategies. For this purpose, a dynamic model was developed to predict the Na and S balance in
the kraft recovery cycle, as well as the accumulation of undesirable non-process elements such as
chlorine (Cl) and potassium (K).
The model was developed using the CADSIM software and was validated using data obtained
from a Brazilian bleached kraft pulp mill. The calculated data from the model showed good
agreement with mill data with respect to all parts of the mill simulated. Dynamic tests designed
to calculate the white liquor sulfidity over specific periods of time also presented good
agreement. The result indicates that the model is able to describe the balance of chlorine,
potassium, sodium and sulfur in the kraft process.
A study conducted to evaluate the Cl and K accumulation agrees with the expected behaviour
observed in mill data. The presence of ash treatment systems allow to reduce Cl and K contents
in recovery boiler precipitator ash from 4.2 mol% Cl(Na+K) to 1.25 mol % and from 2.25 mol %
K/(Na+K) to 0.8 mol% for 100% ash treated. The tests performed for Na and S balances focused
ii
in the makeup requirement for two situations: ash purging and ash treatment to control Cl and K
levels. The use of ash treatment systems reduced Na and S makeup requirement from 5 to 50%
depending on the amount of ash treated.
A simple mathematical model was then used to estimate the Cl balances around the recovery
cycle. Given that the proper simplifications are applied, the CADSIM model and the CSTR
model presented good agreement in estimating the Cl balances. This result provided not only
another method for the CADSIM model to be validated but also a way to calculate a rough
estimate for Cl balance.
iii
Acknowledgements
I would like to thank Professor Honghi Tran, my supervisor, for his guidance. His admirable
work integrating academy and industry gave me an incredible opportunity to learn how to apply
the knowledge obtaining during these years at the university to solve practical problems. He is
an example of leadership for the students who worked with him.
I thank the financial support of the members of the research consortium on Increasing Energy
and Chemical Recovery Efficiency in the Kraft Process, specially the Aracruz mill for
providing me the data needed to complete this project, and the Natural Sciences and Engineering
Research Council of Canada (NSERC). I am grateful for the help provided by Larry Wasik of
Aurel Systems during the course of this work; Larry helped to clarify questions about CADSIM
and provided great advices on model development and validation.
I thank my mother Ana and my father Braz, my sister Miriam and my brother-in-law Angelo for
their encouragement and support in all moments.
Finally, I would like to thank all friends who contributed in some way to this work, specially,
those who helped me with this final document.
iv
Table of Contents
Abstract
Acknowledgements
Table of Contents
List of Tables
List of Figures
List of Appendices
Nomenclature
ii
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vii
ix
xii
xiii
1. INTRODUCTION
1.1 Kraft Pulping
1.2 Chemical Balances in the Chemical Recovery Cycle
1.3 Ash Purging and Ash Treatment
1.4 Objectives
1
1
3
4
4
2. LITERATURE SURVEY
2.1 Introduction
2.2 Sodium and Sulfur Balance
2.2.1 Sulfur Losses
2.2.2 Sodium and Sulfur Makeup
2.2.3 Chlorine Dioxide Effluent
2.3 Chlorine and Potassium Balance
2.3.1 Enrichment Factor
2.3.2 Factors Affecting the Enrichment Factors
2.3.2.1 Lower Bed Temperature
2.3.2.2 Black Liquor Composition
2.3.2.3 Concentration of SO2 in the Flue Gases
2.3.2.4 Amount of Combustion Air
2.3.2.5 Release of Inorganic Compounds
2.3.3 Ash Treatment and the Chlorine and Potassium Balance
2.4 Process Simulation in the Pulp and Paper Industry
2.4.1 Simulation of Kraft Mill Chemical Balance
2.4.2 Pulp and Paper Simulators
2.5 Analysis of the Literature Survey
5
5
5
6
9
9
11
12
13
14
14
15
15
16
17
18
20
21
23
3. METHODOLOGY
3.1 Evaluation of Pulp and Paper Simulators
3.1.1 CADSIM Programming
3.1.2 Modules Implementation into CADSIM
3.1.2.1 Ash Treatment Block
3.1.2.2 Lime Kiln Model
3.1.3 Chemical Balance Model Validation Mill Case Study
3.1.3.1 Data Availability
3.1.3.2 Data Processing
3.1.3.3 Steady State and Dynamic Simulation of the Mill
3.2 Cl and K Enrichment Factor Simulation
3.2.1 EPAC Model
3.2.2 Determination of Inorganic Release
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38
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108
8. CONCLUSIONS
109
9. RECOMMENDATIONS
110
10. REFERENCES
111
11. APPENDICES
119
vi
List of Tables
Table 2.1 - Summary of ClO2 Generation Processes
10
11
25
28
28
30
37
50
50
51
54
56
Table 4.6 - Comparison of Enrichment Factors Determined by EFR Tests and the Model
60
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viii
List of Figures
Figure 1.1 - Schematic Diagram of the Kraft Process
Figure 2.1 - Sodium and Sulfur Losses from the Chemical Recovery Cycle
Figure 3.1 - Block Diagram for Six-Effect Evaporator Process Simulated in WinGEMS
26
Figure 3.2 - Block Diagram for Six-Effect Evaporator Process Simulated in CADSIM
27
Figure 3.3 - Recovery Boiler Model for Energy and Material Balance in WinGEMS
29
30
33
35
39
42
43
45
45
47
49
51
Figure 4.3 - Chloride and Potassium Enrichment Factors as Function of Combustion Air
52
Figure 4.4 - Na, K and Cl Release from Char Bed as a Function of Combustion Air at
1000C
53
55
55
57
59
ix
62
Figure 5.2 - Comparison of Ash Solubilities Given by OLI and the Neural Network
63
64
64
Figure 5.5 - Comparison between Simulated and Mill Values for Evaporation Plants
70
70
Figure 5.7 - Comparison between Simulated and Mill Values for Recovery Boilers
74
75
Figure 5.9 - Comparison between Simulated and Mill Values for Causticizing Plants
80
Figure 5.10 - Comparison between Simulated Values and Mill Value for Full Mill
Simulation
81
82
82
Figure 5.13 - Sulfidity Change Test due to a Short Period Shutdown of ClO2 Plant
83
Figure 6.1 - Determination of Steady State Condition for Cl and K Ash Concentration
88
89
90
91
91
Figure 6.6 - Time for Cl and K Concentration to Reach Steady State for Different
Inventory
92
Figure 6.7 - Accumulation of Cl and K in the Precipitator Ash 5, 10 and 20% Ash
Purging
93
Figure 6.8 - Accumulation of Cl and K in the Precipitator Ash 5, 10 and 20% Ash
Treated
94
Figure 6.9 - Cl and K Levels in the Precipitator Ash for Different Portion of Ash
Treated
94
Figure 6.10 - Na and S Makeup Requirement to Maintain 29.5% Sulfidity (AA) 33%
Ash Purging
96
Figure 6.11 - Na and S Makeup Requirement to Maintain 29.5% Sulfidity (AA) 33%
Ash Treated
97
Figure 6.12 - Total Makeup Requirement for Different Fractions of Ash Purged
98
Figure 6.13 - Total Makeup Requirement for Different Fractions of Ash Treated
98
102
102
Figure 7.3 - Graphic Representation of Equation 7.9 with C0 = 0, Cin = 4kg/m3 and f =
3.5m3/day
104
Figure 7.4 - Comparison of CADSIM data for Cl Accumulation Test and Equation 7.9
assuming C0 = 0, Cin = 4.2kg/m3 and f = 3.5m3/day
105
106
108
xi
List of Appendices
Appendix A - FactSage Software
120
122
124
125
131
149
xii
Nomenclature
Qo = Initial amount of Cl dissolved in tank (kg)
V = Tank volume (m3)
f = Flow rate of input stream (m3/s)
Cin = Input concentration of Cl in the tank (kg/m3)
dQ/dt = Rate of change of Cl amount in the tank
Q = Amount of Cl at any time (kg)
t = Unit of time (s)
K = Constant of integration
xiii
1. Introduction
1.1 Kraft Pulping and the Chemical Recovery Process
Kraft process is the most important chemical pulping process in which the cellulose fibres are
extracted from wood through the use of chemicals. An overview of the kraft process is shown in
Figure 1.1. Kraft mills typically use wood that has been debarked and chopped into chips. In the
first step of the process, the wood chips are sent to a digester where they are mixed with cooking
liquor, also known as white liquor. The white liquor is an aqueous solution mostly composed of
sodium hydroxide (NaOH) and sodium sulphide (Na2S) [1].
After cooking, cellulose fibres are separated from the liquid and washed to make pulp which
corresponds to the second step of the process in Figure 1.1. The liquid obtained after the
separation of the pulp is known as black liquor. Black liquor contains two fractions: organic and
inorganic. The organic fraction is a mixture of lignin, hemicellulose and other dissolved material
from wood, while the inorganic fraction is mostly composed of the residual cooking chemicals.
In order to make kraft pulping economically feasible, the cooking chemicals have to be
recovered, which is accomplished by the chemical recovery process [2].
The chemical recovery process has two parts: the first involves the concentration and combustion
of the black liquor which removes the organic portion of the liquor. The second part of the
recovery process is the causticizing of the inorganic chemicals produced after the combustion of
the liquor.
The concentration of the black liquor is typically done in a multiple effect evaporation system
indicated as step 3 in Figure 1.1. The black liquor is concentrated from 15% to over 70% dry
solids. The concentrated black liquor is then burnt in a recovery boiler in the fourth step of
process. The combustion is used to generate steam and to convert sodium and sulfur compounds
into Na2S and Na2CO3 [3].
The Na2S and Na2CO3 form a molten smelt at the bottom of the recovery boiler. From there the
smelt pours into a smelt dissolver, where it is mixed with diluted white liquor, producing green
liquor. The green liquor is pumped to the slaker where reburned lime (mainly CaO) is added and
slaked lime (Ca(OH)2) is formed. The resulting calcium hydroxide reacts with Na2CO3 in the
2
green liquor, converting it into NaOH and precipitating CaCO3 (lime mud). This reaction takes
place in step 5 of Figure 1.1.
Lime mud is separated from the liquor by filtration or by sedimentation. It is then washed,
dewatered, and fed to a lime kiln where it is calcined to reburned lime (step 6 in Figure 1.1). The
liquor obtained after separation is the white liquor which is the final product of the recovery
process and can be reused as cooking liquor in the digester.
4
including increased TRS (total reduced sulfur) and SO2 emissions, and increased corrosion of
equipment [7].
1.4 Objectives
This research project aims at obtaining the necessary information to calculate sodium and sulfur
balances in the kraft recovery cycle. Attention will be given to mills using ash treatment systems,
since they can act as a purge point for sodium, sulfur, chloride and potassium. This work,
however, would require an evaluation of the effects of ash treatment and makeup practices over
time.
The objectives of this study are:
1)
to develop a model that can predict the Na, S, Cl and K balances in the chemical
recovery process over time,
2)
2. Literature Survey
2.1 Introduction
The previous chapter highlights the need for proper concentrations of NaOH and Na2S in the
white liquor to produce pulp with desired characteristics. The challenge in this task lies in two
facts: first, there is no consensus on the proper amounts of NaOH and Na2S, or in other words on
the sulfidity of the white liquor. Here is important to mention that sulfidity is the parameter used
in kraft mills to monitor the balance of NaOH and Na2S in the liquor. Sulfidity is calculated by
dividing the weight of sodium sulfide (expressed in g/l on Na2O basis) by the weight of sodium
hydroxide plus sodium sulfide (also expressed in g/l on Na2O basis) multiplied by 100.
Second, the sulfidity varies from mill to mill and over time due to chemical losses. The proper
concentrations of NaOH and Na2S are then adjusted by adding makeup chemicals to the recovery
area. However, the makeup addition is not a standardized procedure, but varies significantly
from mill to mill. As an example, process supervisors may adopt a strategy based on a shift or
daily basis, the chemicals used may change depending on cost and availability, which makes the
control of sulfidity a difficult challenge.
This chapter provides background on the difficulties of maintaining the proper Na and S balance.
In addition to that, the chapter considers the problem of accumulation of unwanted chemicals
such as Cl and K responsible for fouling and corrosion in mills. Then, a survey of pulp mill
modelling and simulation is presented, including the few studies dedicated to simulate the
balances of Na and S. The final analysis highlights the need for a tool to deal with chemical
balance problems.
6
To keep the right ratio of sodium and sulfur in the mill, chemicals are added in the recovery
cycle as makeup to the losses that happen along the process. Chemical losses from the process
can occur through different streams: liquor spills, pulp, grits, dregs, white liquor used in
scrubbers, liquor swap with other mills, recovery boiler stack gas and lime kiln stack gas, etc.
[14]. The amount and type of makeup chemicals used in a mill depends on many factors: the
availability and cost, the sulfidity of the cooking liquor, the tolerance with regard to odor and
corrosion problems [15].
The rule of thumb was to add enough Na2SO4 makeup to maintain the sodium content of the
liquor. The excess sulfur thus introduced would leave the system, mainly as SO2 from the
recovery furnace [16, 17]. However, due to environmental regulations now restricting levels of
many chemical discharges, mills need to reduce effluent by recycling streams back to the process
[18, 19]. One example of stream is the saltcake produced at the ClO2 generators [20].
7
DNCG. The stripper gases are typically composed of 50% water vapour and 50% methanol, and
minor portions of TRS, ethanol and turpentine.
Due to the high sulfur content, NCG needs to be completely oxidized before it can be released to
the atmosphere. To burn NCG, three conditions must be met: temperature of 760C, residence
time of 0.5 s and excess oxygen (3 to 4%) [1]. In a pulp mill these conditions can be found in
four places: lime kiln, power boiler, recovery boiler, and dedicated incinerators. Burning NCG in
the lime kiln is interesting because the lime mud can absorb SO2; however there is a limit [22]. If
the kiln fuel has also high sulfur content, some sulfur gases can be emitted. Power boilers and
recovery boilers can burn NCG; however, this option must be carefully considered to avoid high
emissions [23-25].
Several authors report data regarding sulfur losses as gases from kraft mills. Bergstrom and
Trobeck [26] determined the loss of volatile sulfur compounds associated with digestion and
blow and showed that the total loss is equivalent to 1 kg of sulfur per ton of pulp. By determining
the ratio of sulfur to total solids in the liquor prior to and following evaporation, they also
estimated the sulfur loss in the evaporation plant to be about 10 kg of sulfur per ton of pulp.
Blackwell and Lincoln [14] performed calculations and estimated the sulfur loss from lime kiln
flue gas around 0.02 kg of sulfur per ton of pulp. Grace and Malcolm [3] provided an average
value of 0.47 kg of sulfur lost per ton of pulp in recovery boiler flue gases by a compilation of
data from different sources. Valeur et al. [27] reported the TRS emissions from black liquor heat
treatment and superconcentrators to be 5.56 kg of S / odt in a case study. Figure 2.1 shows the
various points of sodium and sulfur losses in the kraft process.
Although the sulfur losses are measured and known in some mills, the task of keeping the right
concentration of sodium and sulfur in the mill remains difficult. The amount of chemicals to be
added in the recovery cycle as makeup changes over time depending on many factors and a
material balance for the whole recovery cycle would be required to allow for proper makeup.
Figure 2.1 Sodium and Sulfur Losses from the Chemical Recovery Cycle [3]
10
ClO2 is always generated on-site because of its unstable nature and risk of rapid decomposition
[31]. In all processes, ClO2 is produced from acid solutions of either sodium chlorite or sodium
chlorate. The chlorate-based processes are preferred due to the lower cost and higher stability of
sodium chlorate compared to sodium chlorite. There are several processes used to generate
chlorine dioxide. Some of them are listed in Table 2.1.
Table 2.1 Summary of Chlorate-based ClO2 Generation Processes
Main Reaction Involved
Process
SO2 Processes:
Mathieson
and Holst
Methanol Processes:
Solvay,R8,
R9 , R10
NaCl Processes:
SVP, R2,
R3 and R7
HCl Processes:
R4, R5,
R6, Lurgi
SVP-HP
SVP-HA
The salt cake formed by these processes is either sodium acid sulfate (NaHSO4) or sodium
sesquisulfate [Na3H(SO4)2]. Most of the saltcake is reused in kraft mills as makeup chemical. In
recent years, however, mills are facing problems due to the high sulfur content of the by-product.
Furthermore, due to its acidic nature, the saltcake must be neutralized before it can be disposed
of, making the disposal process costly [32].
To avoid disposal, the best option is to use the saltcake generated, which can lead to excess
sulfur in the process depending on the amount recycled to the chemical recovery. The challenge
is that the composition and the amount produced vary widely depending on the process used as
shown in Table 2.2. Increasing sulfur recycle increases sulfur gas emissions and liquor corrosion.
11
Table 2.2 Amount of By-products from ClO2 Generators [33]
ClO2 Production
NaCl
Cl2
Na2SO4
H2SO4
Process
(t/ tClO2)
(t/ tClO2)
(t/ tClO2)
(t/ tClO2)
Mathieson
1.42
1.72
Solvay
1.31
1.60
R2
0.57
2.27
3.28
R3 / SVP
0.66
2.27
0.66
1.36
R5 / R6 / Lurgi
0.95
0.90
R8
1.36
0.11
R10
1.06
One way to avoid the reuse of the saltcake and the Na/S imbalance generated is to reduce
saltcake byproduct in the ClO2 production process. Many studies are devoted to improve the
ClO2 generation, however only recently some researchers have focused on the possibility of
saltcake free process [32, 34].
In order to manage properly the excess sulfur mills produce chemicals on-site to balance any
excess of sodium or sulfur. The focus here involves two alternatives. One developed at FP
Innovations makes use of a resin to produce NaOH and H2SO4 from saltcake produced by the
ClO2 generators [35]. The other developed by Kvaerner Chemetics involves the production of
sulfuric acid using the NCG collected from the different points in the mills [27].
Finally the most common practice to deal with excess chemicals is to dispose off the precipitator
ash and correct any imbalance by adding makeup for Na or S [11]. This procedure may be costly
due to the increasing cost of chemicals, but with the help of a precise material balance it may
provide a way not only to control Cl and K contents in the recovery area but also reduce Na and
S imbalances.
12
liquor is usually between 0.5 and 0.7 wt% on dry solids, but may exceed 2 wt% for mills where
wood is floated in sea water [36 - 38]. Other sources of Cl are makeup chemicals and effluent of
the bleach plant that is sent to the recovery cycle.
Because of the negative effect of Cl and K, their concentrations are measured in many different
streams around the recovery cycle. The problem is that many units are employed to report Cl and
K concentrations, and these units vary significantly from one mill to another. In some mills,
grams of NaCl per liter is used to measure Cl content in white liquor; in others, g/L of Cl, parts
per million (ppm) of Cl, ppm of NaCl, wt% of NaCl, fractional units such as Cl/Na and
Cl/(Na+K) ratio are also used. Such a wide variety of units makes comparing Cl and K
concentrations from different mills very difficult, and to assess whether or not Cl and K will be
an issue in a particular case [36].
13
enrichment factor for Cl (EFCl) is around 2.5, while for K (EFK) is around 1.5; but can change
depending on the operating conditions of the boiler [36]. The enrichment factor for Cl is given
by equation 2.1 and for K in equation 2.2:
Cl
Na K
ash
(2.1)
EF
Cl Cl
Na K BLSolids
Na K ash
(2.2)
EFK
K
Na K BLSolids
The distribution of Cl and K compounds between smelt and gas phase depends on the operating
conditions in the recovery boiler. Char bed temperature, combustion air flow rate, black liquor
composition, SO2 concentration in the gas phase and inorganic release from black liquor droplets
are believed to play a major role in the Cl and K enrichments. Since Cl and K lower the melting
temperature range of the particulate matter in the upper boiler region, making it stickier,
understanding how the boiler parameters affect the enrichment factor would be important in
helping to manage possible plugging problems in the recovery boiler.
14
(2.3)
This reaction would lead to the release of metallic sodium and carbon monoxide, the metallic
sodium would then react and form sodium sulfate and sodium carbonate that are found in the
ash. At lower temperatures, the enrichment factors would also increase, due to lower amounts of
sodium present in the ash.
15
16
Although the amount of combustion air is believed to affect the enrichment factors of Cl and K,
no systematic study has been done to evaluate this effect. Reis et al., Janka et al. and Frederick et
al. [39, 40, 44 and 51] mentioned that the amount of combustion air is critical to the enrichment
factors, but how the combustion air amount affects the enrichment factors was not clearly shown.
(2.5)
17
where the suffix (c) denotes a condensed phase (solid or liquid) and (g) for gas phase. At the
combustion temperatures and in the presence of O2 and H2O, the Na vapor is rapidly converted
to NaOH as in reaction 2.6:
2Na(g) + 1/2O2(g) + H2O(g) 2NaOH(g)
(2.6)
Potassium is released through analogous reactions from K2CO3. The hydroxide vapors then react
with the SO2 as indicated in reaction 2.7:
2NaOH(g) + SO2(g) + 1/2O2(g) Na2SO4(g) + H2O
(2.7)
Finally the chlorine is present in black liquor mainly in the form of chloride ion. Thus, the
accepted dominant mechanism of Cl release is direct vaporization of NaCl and KCl as in
equation 2.8:
NaCl(c) NaCl (g)
(2.8)
Considering the wide range of values that the variables discussed such as char bed temperature,
liquor composition and combustion air flow can assume and how they interact with each other in
the boiler, it would be helpful to create a model to simulate the ash formation process and
evaluate the impact of each parameter on the Cl and K enrichment factors. This task would
require the use software capable of dealing with the thermodynamic of the systems found inside
the recovery boilers.
18
containing sodium and sulfur would remain in the solid phase being recycled to the recovery
area.
Thus, in order to simulate the chlorine and potassium balances for mills using ash treatment
processes, it is necessary to obtain the operating conditions of the process and its influence on
the composition of the purged stream. Due to the complex thermodynamic calculations involved
in this task, ash treatment blocks are unavailable in any pulp and paper process simulator. To
overcome this problem, a databank containing information regarding the ash treatment
performance for different ash compositions, ash-to-water ratios and temperatures was built using
the OLI software [63].
The OLI Software [64] is a commercial package used to calculate thermodynamic properties of
aqueous systems. It is generally used for predicting complex chemical and electrochemical
phenomena in aqueous and mixed solvent environments. The predictive thermodynamic model
in OLI is based on published experimental data for many chemical mixtures over a wide range of
temperature (-50 to 300C), pressures (0 - 1500 bar), and ionic strength (0 - 30 molal).
Unfortunately, the information gathered from OLI can not be readily incorporated into most pulp
and paper simulators. Thus, an ash treatment block should be developed in order to implement
the ash treatment system into a model for the whole kraft chemical recovery. The block was
developed using a neural network module as described later.
19
require more thorough and detailed models; on the other hand, mill models that are used to
explain the overall behaviour of the process employ much simpler models. Thus, in the planning
of the simulation studies, the purpose of the simulation and the requirements for the results must
be considered beforehand to make sure that suitable models are being used and the data required
for the model validation is available.
Models for mill simulation should not be designed as a compilation of models employed to study
specific processes within the mill [65]. Because of process models usually present excessive
amount of equations and variables that would be useless for an overall simple balance. As a
result, they increase the margin for error and make a complete balance checking difficult, since
some variables may not be measured by the mills [28].
A vast number of papers have been published concerning the modelling and simulation of the
pulp and paper processes. Johnsson [66] and Wisnewski [67] developed models to simulate the
kraft cooking process. Norden and Jarvelainen [68] modeled the pulp washing process by drum
filters, while Turner et al. [69] and Wasik et al. [70] studied the countercurrent diffusion
washing. Kinetic models of pulp bleaching have been developed by Edwards et al. [71] and a
simulation model developed by Rouda et al. [72]. Bremford et al. [73-75] constructed models for
the black liquor evaporation plants. Galtung [76] and Costa [77] have developed mathematical
models to simulate recovery boilers. Modelling and simulation of causticizing plants have been
built by Beckwith [78] and Swanda et al. [79]. Lime kiln models were presented by Edwards et
al. [80] and Georgallis et al. [81].
On the other hand, whole mill modeling is more difficult due to the fact that two identical pulp
and paper mills do not exist. This forces the programmer to change the available models so that
they can be used for a particular case in question. How successful the model is will depend on
the fitting of calculated parameters to the actual mill measurement. One example involving an
economic study around a kraft cycle is presented by Venkatesh et al. [82]. Another study by
Gunseor and Rushton [83] evaluated alternatives to reduce energy requirements. Jordan and
Bryant [38] studied Cl and K concentrations in the liquor around the kraft cycle. With respect to
the simulation of the kraft mill chemical balance, which is subject of interest in this study, only a
handful of studies were developed and published. Due to the different perspectives adopted by
20
the authors, very different conclusions were drawn from their results as it is shown in the next
section.
(2.9)
This is an endothermic reaction. The energy required for it to occur is taken from the combustion
of black liquor fed into the boiler. Clearly, as sulfur content in the liquor decreases, less energy is
consumed by the reaction and greater proportion of the heat is available for steam generation.
On the other hand, at a low sulfidity the smelt leaving the recovery boiler contains more sodium
carbonate which must be converted to sodium hydroxide in the causticizing plant to complete the
chemical recovery process as indicated by the reaction 2.10:
Na2CO3(l) + Ca(OH)2(s) 2NaOH(l) + CaCO3(s)
(2.10)
21
Most of the lime required is produced by a kiln through calcination of limestone:
CaCO3(s) CaO(s) + CO2(g)
(2.11)
The increased amount of Na2CO3 results in an increase in kiln load and hence in kiln fuel
requirement. Lime losses would also be higher since more material is being handled [93]. Thus
the increased costs in the causticizing plant may offset the gains made in the steam generation at
the recovery boiler as discussed by Baldus and Edwards [94].
Thus the choice of sulfidity levels is done based on economic aspects, which makes the
definition of a single targeted value for sodium and sulfur content not realistic. The parameters
considered in the decisions usually involve the cost of energy, wood, lime kiln fuel, makeup
chemicals and bleaching chemicals. This cost analysis led to very distinct approaches to the
sulfidity levels in different parts of the world. As an example, Boyle and Treiber [92] suggest
that 25% sulfidity (AA basis) would be a favourable operating condition for mills in North
America; while Sondell [95] claim that the optimum sulfidity would be 40% for Scandinavian
mills. Thus in order to analyse the different aspects involved in the sodium and sulfur balance it
is important to have a model that can evaluate the whole mill before any sulfidity level can be
suggested.
22
kraft mill model using this simulator. WinGEMS and GEMCS are steady-state simulators and
employ a sequential method of solution to calculate the output variables of the models.
MASSBAL MKII was originally developed by SACDA Inc. in cooperation with Energy Mines
and Resources Canada as a generalized simultaneous modular process simulation package for
calculating the steady-state heat and mass balances for industrial processes [98]. The system has
been designed for the modeling of water-based processes such as those found in pulp and paper
and mineral industries. In the 1990s, MASSBAL MKII became CADSIM after the copyrights of
the program were acquired by Aurel Systems. Further developments permitted CADSIM to
generate models for different processes. As the software continued to evolve, Aurel Systems
developed and released CADSIM Plus [99].
The software now uses a sequential solver for performing dynamic simulations. This means that
each unit and stream is executed in sequence, through an iterative step in time. The default
sequence that CADSIM Plus uses when executing the units and streams is usually the order in
which they were created. However, if needed, the software allows for the programmer to interact
with the model and change this sequence. Usually this may happen if modules are not executed
in order of flow, what can create artificial time lags in the model and affect the simulation
response and stability.
In each simulation iteration step in time, the following calculation steps are followed: (i) all
specifications are calculated, except network specifications, (ii) each unit module is calculated in
the order that it appears in the drawing, with the exception of a unit module that has a network
flow [99]. In this case every unit module in that particular network of process flows is iterated in
a loop until a convergence is reached. Once converged, the execution passes on to the next unit
module.
It is important to mention that there all previous work published involving the chemical balance
of kraft mills was developed using steady-state simulators. Since the objectives of this study is to
determine the impact of the ash treatment and the various makeup sources on the chemical
balance, it is necessary to evaluate these changes as they occur over time. In order to achieve
these goals, a dynamic simulation has to be done, which makes the CADSIM Plus package more
suitable to be used in this project. However, the software will need to be used together with other
packages to be able to perform some specific calculations not originally present in its library
23
such as the enrichment factor calculation which is calculated using FactSage simulator described
in Appendix A.
2.5 Summary
As explained previously, one of the difficulties with keeping the proper sulfidity (NaOH and
Na2S concentrations) lies in the fact that the recovery process has many losses. In some of them
sodium is associated with sulfur while in others sulfur independently leaves the process in gas
phase. As a result the balances of Na and S will differ from mill to mill and over time.
Simultaneously, the makeup available for mills to counterbalance the losses is also different in
composition and amount. Therefore, each mill would require an individual evaluation to allow
for a proper makeup strategy.
In addition to the Na and S balance problems, the accumulation of unwanted chemicals such as
Cl and K has become a growing concern to the mills. Since mill processes are being tightened up
to reduce losses and meet environmental regulations, non-processes elements concentrations are
increasing to levels where they become harmful to equipment and processes. In the case of Cl
and K that are soluble in the mill liquors the best option is to use the electrostatic precipitator
ash. Since the ash is enriched in Cl and K and is composed of salts containing Na and S this
stream could be not only a point to purge Cl and K but also to adjust the Na and S
concentrations. This would be possible if the ash is treated to obtain the maximum removal of Cl
and K, with the needed amount of Na and S recycled back to the process.
Finally, evaluating all work developed around the simulation in the pulp and paper industry, it is
clear that most works focus on the understanding and optimization of individual processes. The
few published works on the whole mill involves separate balances of Na and S or Cl and K.
What is required for a deeper understanding of the process is a model to account for the balance
of Na, S, Cl and K together with the alternative to use the ash treatment system as a control point
for Na and S balance and Cl and K purge. In addition to the 4 elements balance, the modeling of
an ash treatment system and the capability of the model to evaluate its impact over time
(dynamic simulation) would make this project a unique contribution to the pulp and paper
industry.
24
3. Methodology
The Methodology section of this work is divided into two parts: the first part describes the
simulation work needed to build the model for a kraft mill chemical balance. Two of the most
common pulp and paper simulators are presented and compared in order to decide which one
would suit better for the task at hand. Once the software is chosen, the simulator programming is
then briefly described and the necessary changes and improvements on the simulator are
presented. Finally the process of model validation is discussed.
The second part involves the simulation of the Cl and K enrichment factor, which is an important
parameter in establishing the balances of Cl and K in the kraft mill liquor cycle. A series of
laboratorial experiments are also performed to validate the model findings as presented in the
later sections of this chapter.
25
sequentially, although alternate numbering schemes are sometimes appropriate. As an example it
is shown below two tests using these simulators, one involves the simulation of an evaporation
plant and the other a recovery boiler based on the blocks available in WinGEMS and CADSIM.
The evaporation plant simulated consists of 6 effects and 7 evaporator bodies (numbered 1A, 1B
and 2 through 6 respectively). Steam is supplied to evaporators 1A and 1B in parallel and the
weak black liquor feed is split between the 5th and 6th effects. The flow is counter-current with
the vapor liberated in the 1st effect used as the heating medium in the 2nd and so on. The clean
condensate is collected and returned to the boiler while the condensed vapor is collected and
either reused or treated as effluent. The strong black liquor is further concentrated and burned in
the recovery boiler. The process conditions are shown in Table 3.1 and are based on data
provided by Bergstrom [100].
Table 3.1- Input Data for Multiple-Effect Evaporator System
Input Data
Parameter
Steam Pressure
Steam Flow
Weak B.L. Flow (x1000)
Weak B.L. Solids
Evaporator Area (1A and 1B)
Evaporator Area (2 to 6)
6th Effect Vacuum
Value
31.5 psig
51.7 klb/h
333 lb/hr
13.93%
4400 ft2
8800 ft2
26 in. Hg
The block diagram representing the problem is shown in Figures 3.1 for WinGEMS simulation
and 3.2 for CADSIM simulation.
Table 3.2 shows the results for the simulations using WinGEMS and CADSIM, as well as the
values calculated by Bergstrom for this problem. The heat transfer coefficients were adjusted to
match evaporator capacity, economy, and strong black liquor solids values. As it is shown the
results are in good agreement between WinGEMS and CADSIM as well as the calculated values
by Bergstrom.
26
Figure 3.1 Block Diagram for Six-Effect Evaporator Process Simulated in WinGEMS
27
Figure 3.2 Block Diagram for Six-Effect Evaporator Process Simulated in CADSIM
28
WinGEMS
244,000
4.76
187
246
423
391
313
233
187
51.4
42.3
34
25.7
21
17.7
18.8
CADSIM
243,980
4.8
177
235
395
388
314
236
187
51.2
42.3
34.1
25.9
21.1
17.8
18.9
Bergstrom [100]
243,840
4.75
174
242
392
386
316
240
190
51.1
42.2
34.6
26
21.2
17.8
19.1
The second test involved the simulation of a recovery boiler. The boiler considered is a bi-drum
model firing 75000 kg/h of black liquor at 70% dry solids and 115C. Air for the liquor
combustion is provided at 150C in three levels with 10% excess for the amount of liquor burnt.
Under normal operating conditions, the boiler would be able to achieve 95% reduction efficiency
generating flue gases at 175C in the stack and smelt at 720C in the spouts leaving the boiler. It
is assumed 3% heat losses and 10000 ppmv CO at stack gas. The remaining useful data needed
to calculate the balances at given process conditions are shown in Table 3.3 and are based on
data provided by Empie [101].
Table 3.3 - Input Data for Recovery Boiler Balance Calculation
Black Liquor Composition (%)
Na
19
C
39
O
33
H
4
Input
Parameters
CpAir (kJ/kgC)
CpSmelt (kJ/kgC)
CpFlue Gas (kJ/kgC)
CpSteam (kJ/kgC)
Value
1.00
1.67
1.00
2.00
Parameters
HWater (kJ/kg)
HRed. (kJ/kg Na2S)
HSmelt (kJ/kg)
HCO (kJ/kgCO)
Value
2554
12900
185
10110
25
CpWater (kJ/kgC)
4.18
Cl
CpBLS (kJ/kgC)
2.09
29
The block diagram used to simulate this problem is shown in Figures 3.3 for WinGEMS
simulation and 3.4 for CADSIM simulation.
Figure 3.3 - Recovery Boiler Model for Energy and Material Balance in WinGEMS
Table 3.4 shows the results for the simulations using WinGEMS and CADSIM.The results show
that CADSIM and WinGEMS are capable of simulating the process even using different model
layouts. Other equipment such as the lime kiln, digester, and clarifiers were also simulated and
the results of both simulators were in good agreement. Thus, choosing one program or the other
depends on the focus of the study. Usually CADSIM is used to study dynamic features, while
WinGEMS deals with steady-state simulation.
30
31
structure WinGEMS cannot perform dynamic simulations. On the other hand, CADSIM can
perform dynamic evaluation of the process, but cannot provide the same in depth analysis of the
process in each piece of equipment.
For the objectives of this study, CADSIM would be more interesting because it could provide
information regarding Cl and K accumulation over time including changes in the concentrations
for different ash treatment operating conditions or ash purging periods. Simultaneously the
impact on sulfidity levels could be studied as Na and S makeup requirement changes.
32
Mode allows CADSIM Plus to create CAD drawings of a process, and to create mathematical
models for the energy and material balance of the process. The Specification Mode is used to
specify process variables in the simulation model. The program passes through the process
drawing and requests information about how the process relationships are defined based on the
stream chemistry provided and the equipment units drawn [99].
When the drawing is fully specified, it can be run in the Simulation Mode. In this mode,
simulation results can be dynamically displayed on the drawing wherever they are specified. Any
drawing component can be fully evaluated during the simulation through dialog boxes that
contain current simulation information for that object. Some important parameters can be stored
in text files and analyzed in dedicated data mining software.
33
Unfortunately, due to differences in software language and structure is not possible to
incorporate OLI into CADSIM to perform the calculations needed to simulate an ash treatment
system. Thus, a module was developed based on the databank obtained from OLI and on a neural
network block available in CADSIM that would act as a tool performing the calculations needed
for the ash treatment simulation.
According to the description on CADSIM, the neural network block is an input-output mapping
module that learns to reproduce functional relationships among variables in a databank [99]. It
is generally composed of a layer of input cells, 1 or 2 layers of hidden cells (called hidden A and
hidden B in Figure 3.5), and a layer of output cells. Every cell on hidden A is connected to the
input cells through the use of weights. Weights also appear between hidden B cells and hidden
A cells, and between output cells and hidden B cells, as shown in Figure 3.5 [99]. These weights
are numeric values that indicate the influence of each cell in the network.
In the process of designing a neural network some important parameters must be decided such as
the topology (number of cells and layers), the learning steps (how weights are changed) and
the stopping criteria (average error acceptable). These parameters vary based on the complexity
of the problem [102]. Given the lack of clear guidance in the literature concerning the selection
of the parameters, a trial-and-error procedure is usually followed [103]. Once the neural network
is designed a set of training patterns is submitted to test. These training patterns are just a set of
input values with their expected mapped output values.
34
Once the training patterns are fed into the module, the network adjusts its weights in response
to the different input patterns so that its actual response converges to the desired output response
[102]. The convergence is governed by the minimization of some error criteria between the
input-output data available and the output returned by the neural network. Once the training
patterns can be reproduced by the network within an acceptable error range, the resulting weight
vector is saved and the network is ready to be validated.
In the validation, the network with the adjusted weights receives a set of patterns different from
the ones used in the training step. Usually this set is part of the original databank where some
patterns were randomly extracted [102]. This set would evaluate the capability of the network to
generalize within the domain of data used.
35
36
process variables used in the assessment of the mill operating conditions. The data resolution for
each variable ranged from hourly-averaged measurements taken by on-line instruments, to milllab data collected as infrequently as a few times per year. A list with the significant parameters
collected for different areas is shown in Table 3.5.
37
Table 3.5 - Variables Collected for Different Mill Areas
Digester
Recovery Boiler
Dregs
ClO2 Generator
NaClO3 Flow
H2SO4 Flow
Methanol Flow
Steam Flow
Reboiler Liquor Temperature
Measured ClO2 Production
Generator Efficiency
Total Production per Day
Generator Pressure
Saltcake Production per Day
Evaporation
Weak Black Liquor Flow to Evap.
Weak Black Liquor Dry Solids
Weak Black Liquor Temperature
Pressure of All Effects
Pressure Surface Condenser
Vapor Temperature Surface Condenser
Dry Solids in the Exit of All Effects
Liquor Temperature at Exit of Effects
Liquor Flow at Exit of Effects
Cooling Water Temperature Condenser
Cooling Water Flow to Condenser
Condensate Flow From Last Effect
Total Steam Flow to Evaporation
Steam Flow to 1st Effect
Steam Temperature to 1st Effect
Strong Black Liquor Flow
Dry Solids Strong Black Liquor
Storage Tank Temperature
Dissolving Tank
Weak Wash Flow
Weak Wash Temperature
Raw Green Composition Analysis
Filtered Green Liquor Total Alkali
Lime Mud Flow to Cassette Filters
Raw Green Liquor Temperature
Green Liquor Total Flow to Filters
Green Liquor Total Flow to X-filters
Total Green Liquor Flow
Causticizing
Lime Flow to Slaker
Green Liquor / Lime Ratio
Slaker Temperature
Contaminated Condensate Washing
Causticizing Efficiency in Slaker
Na2CO3 in Slaker
NaOH in Slaker
Na2S in Slaker
Total Flow of Condensate
Lime Consumption
Liquor +Mud Composition Analysis
Total White Liquor Flow
White Liquor Composition Analysis
Cl in White Liquor to Digester
CaCO3 in White Liquor to Digester
K in White Liquor to Digester
Na2CO3 in White Liquor to Digester
NaOH in White Liquor to Digester
Na2S in White Liquor to Digester
Lime Kiln
Lime Mud Flow to Kiln
Lime Mud Density to Kiln
Lime Mud Dry Solids to Kiln
Lime Mud Composition to Kiln
Fuel Flow to Kiln
Fuel Pressure to Kiln
Fuel Temperature to Kiln
Air Flow To Kiln
Air Pressure to Kiln
NCG Burning in Kiln
Kiln ID-Fan Speed
Kiln Zone Temperatures
Reburned Lime Composition
Kiln Production
O2 in Kiln Flue Gas
TRS in Kiln Flue Gas
CO in Kiln Flue Gas
Flue Gas Temperature
38
39
40
41
All gases are ideal;
Equilibrium is attained in both the reducing and oxidizing zones;
No physical carryover is entrained in the flue gas in the upper furnace;
Smelt is completely separated from the flue gas in the lower furnace;
Water and other releasable components in the black liquor are released immediately as the
liquor is sprayed into the boiler and become vapors or gases which are perfect mixed with the
flue gas in the oxidizing zone.
The FactSage used in the EPAC model is the version 6.2. It consists of a series of modules that
access various updated thermodynamic databases in order to perform calculations using a Gibbs
free energy minimization technique.
As shown in Figure 3.8, the calculation is performed as follows. The amount of combustion air
(stoichiometric air demand) needed to burn the black liquor is obtained based on the as-fired
black liquor composition and flow rate (Stream 1). The calculated amount of air is divided
between the oxidizing zone (Stream 4) and reducing zone (Stream 7) according to the desired air
ratio (Stream 2). A portion of black liquor, which has been released in the reducing zone during
drying and pyrolysis, enters the oxidizing zone (Stream 5), while the rest of the black liquor
(Stream 6) enters the reducing zone.
Using the combined input data from Streams 6 and 7, FactSage calculates the amount and
composition of the smelt in the lower furnace, as well as the amount and composition of the gas
phase at a given bed temperature. This equilibrium gas phase (Stream 8) is transported to the
oxidizing zone where it is mixed with the remaining combustion air (Stream 4), the black liquor
components released during devolatilization and pyrolysis (Stream 5) and the excess air used in
the upper furnace (Stream 3). FactSage then recalculates the amounts and compositions of the
gas (flue gas) and solids (precipitator ash) at 160C.
42
43
44
mass flow rate of approximately 5 g/min to the top of the particle injector. The injector
introduces the particles into the top of the heated section and is used to produce a hot flue gas
stream, which entrains the particles and passes through the reactor. The gas combustion chamber
is located at the top of the heated section and is equipped with a natural gas burner, which
consumes natural gas at flow rate of 1 to 2.5 standard m3/h. The combustion gases produced are
mixed with dilution air to produce gases with temperatures up to 1200C. The heated section is
an assembly of five tubular furnaces 1.22 m high with 30 cm of internal diameter that can be
electrically heated up to a maximum of 1350C. Between adjacent furnaces, there is a 10 cm
high observation port installed. These assembly results in heated section 6.5 m long that provides
a hot environment for the black liquor particles to burn. The non-heated section consists of an
insulated chamber located between the bottom of the heated section and the exhaust system. The
chamber has two half cylinders 23 cm high which closes around the probe where samples can be
collected for analysis. In total the entrained flow reactor extends for 9 m from the top of the
particle feeder to the bottom of the exhaust system [105].
The tests performed in this reactor consisted in setting the heated section at the desired
temperature (tests were run at 800C and 900) and allowed to reach steady state (usually period
of 12 hours). The 5 black samples, prepared as mentioned in Appendix C, were sieved to ensure
that the particles were smaller than 90 m and then fed to the reactor. The particles burned as
they traveled downward with the hot flue gas stream through the heated section of the EFR. The
fume formed during the combustion process is collected from the reactor using a fume sampling
device showed in Figure 3.10. The fume sampling device consists of a stainless steel tube 70 cm
long and 1.6 cm I.D. with a filter placed at the middle of the device and a vacuum pump at one
end. The device is placed at the non-heated section of the reactor in order to collect the fumes
exiting the heated section. The purpose of the fume sampling device is to reduce contamination
with carryover, which affects significantly the enrichment factor measurement, by sucking the
fume gases from the non-heated section before they condense.
The samples collected are then dissolved in water and analyzed for sodium, potassium, chloride,
sulfate and sulfide content. Each experiment was run in triplicates.
45
3.3 Summary
As an overview of this chapter it would be interesting to highlight the different steps taken
towards the completion of this work. The first part includes the development of the model
involving the use of CADSIM built-in models, the EPAC model developed using FactSage and
the neural network to generate the ash treatment block using data provided by OLI. A simplified
diagram of this part of the thesis work is shown in Figure 3.11.
46
The next step was the CADSIM-based model validation as described in section 3.1.3.3 and in
Figure 3.7. The model validation results include the steady state simulation of mill areas, the full
mill steady state simulation and the dynamic calculation of the white liquor sulfidity. The results
are discussed in Chapter 5.
After the model was validated, a sensitivity study was performed in some parameters that would
affect the Cl and K balance. The variables chosen included the Cl and K input to the process, the
soda inventory of the mill and the use of ash treatment or ash purging. The impact of ash
treatment or purging was also considered in the study of Na and S balance as well as the impact
of different ClO2 generator effluent. These results are presented and discussed in Chapter 6.
Finally, Chapter 7 presents a simplified mathematical model that can be used to provide
estimates on the balances of Cl and K for a generic recovery cycle. An overall diagram for this
thesis work is seen in Figure 3.12.
47
48
49
samples for a set of specific conditions. Once this information was obtained, the final model
could be used in the study of the factors affecting the Cl and K enrichment factors.
The release factors of the inorganic compounds present in the black liquor were determined
experimentally for 5 different black liquor samples with compositions as indicated in Table 4.1.
The tests consisted of exposing the dried samples to a desired temperature (400 to 900C) for a
period of 60 seconds. The residue remaining after the combustion is then analyzed and the
amount of remaining inorganic chemicals is compared to the initial mass in the black liquor. This
experiment would provide information on the amount of inorganic chemicals lost by the black
liquor droplets during the time they travelled from the black liquor guns to the lower bed. A
graph showing the variation of the release factor as a function of temperature for one sample is
shown in Figure 4.1. As it can be seen, at high temperatures the release values are higher due to
the vaporization of part of the inorganic chemicals, but as the test temperatures are reduced the
release values level off identifying the release factor value. Other curves were obtained for all 5
black liquor samples for the range of temperatures considered.
20
15
Cl
K
10
Na
5
0
400
500
600
700
800
900
50
Table 4.1 Black Liquor Composition (wt% - dry basis)
Element
Sample 1
Sample 2
Sample 3
Sample 4
Sample 5
Na
18.71
18.58
18.29
18.00
18.04
2.46
3.06
3.10
1.06
2.84
Cl
0.54
0.41
0.15
0.18
1.68
4.65
3.06
4.01
5.05
5.20
The release factors obtained from the flat part of the curves were averaged among the tests
conducted in triplicates and are shown in Table 4.2. They will be used in the validation tests
conducted in the entrained flow reactor discussed in section 4.3. These values were then
compared to literature values obtained from various sources [40, 52, 55-57, and 100].
Table 4.2 Average Value of Experimental Release Factor
Element
Sample 2
Sample 3
Sample 4
Sample 5
Na
5.1 2.5
8.3 2.5
7.0 2.5
9.1 2.5
7.7 2.5
6.2 2.5
9.5 2.5
12.7 2.5
10.3 2.5
10.7 2.5
Cl
7.5 5.0
14.4 5.0
15.1 5.0
13.7 5.0
12.8 5.0
24.6 5.0
25.9 5.0
25.0 5.0
25.5 5.0
24.8 5.0
Although on average the release factors are close, the exact values vary from liquor to liquor.
The different release factors found among liquors is attributed to the fact that these elements can
be in the form of different compounds in the black liquor. For example, organically bound Na
and S are expected to be released readily when thermal decomposition starts. On the other hand,
the release of inorganic Na and S will be dependent on which compounds they are. For example,
residual NaOH would be relatively easy to vaporize, while Na2S or Na2SO4 may not be released.
51
lower bed, raging from 30 to 70%. The black liquor characteristics considered are three different
Cl and K contents and two sodium-to-sulfur ratios (S/Na2). In all cases, the excess air was fixed
at 20%, and the pressure throughout the boiler was set to 1 atm.
Composition (wt %)
33.90
3.90
35.80
20.30
5.10
0.80
0.20
Enrichment Factor
3.0
Cl
2.0
K
1.0
0.0
800
900
1000
1100
1200
1300
Temperature (C)
Figure 4.2 - Chloride and Potassium Enrichment Factors as a Function of Temperature
Combustion Air = 30%; Composition: Cl=0.2%, K=0.8%, S/Na2 = 0.35
52
Figures 4.2 show how bed temperature affects the enrichment factor for Cl and K. The
enrichment factors initially increase as the lower bed temperature increases until a maximum of
2.7 for Cl at 1050C and 1.7 for K at 1100C. At higher temperatures, the enrichment factor
decreases due to two factors: the first is that Cl and K are depleted in the char bed due to lower
concentrations; the second is that, at high temperatures, the amount of Na release becomes
significantly larger than the amounts of Cl and K which cause a dilution effect resulting in a
lower EFCl and EFK as pointed out by [40].
Enrichment Factor
4.0
3.0
Cl
2.0
1.0
0.0
30
40
50
60
Combustion Air (% Theoretical Air)
70
Figure 4.3 - Chloride and Potassium Enrichment Factors as Function of Combustion Air
Temperature =1000C; Composition: Cl=0.2%, K=0.8%, S/Na2 = 0.35
Calculation results show that if the combustion air flow is lower than 30%, a significant amount
of char will be present in smelt due to incomplete combustion. On the other hand, if the
combustion air flow is higher than 70%, it lowers the reduction efficiency, which is undesirable.
53
Figure 4.3 indicates the effects of combustion air on the Cl and K enrichment factors at 1000C.
As the combustion air increases, the enrichment factors increase. Janka et al. [40] suggested that
combustion air had an effect on Cl and K enrichment factors, but they did not show what the
effect was. In this study, EFCl increases from 2.4 at 30% to 3.5 at 70%, while EFK increases from
1.3 at 30% to 1.4 at 70%.
Based on the results obtained from the model, it seems that the increase in enrichment factors is a
result of lower Na release from the lower bed as in Hupa [48]. As shown in Figure 4.4, the total
amount of Na released at 1000C decreases with an increase in combustion air flow, whereas the
concentrations of the species containing chlorine (i.e. NaCl and KCl) do not change appreciably.
The release of K is similar to that of Na, explaining the more pronounced variation in the Cl
enrichment factor compared to that in the K enrichment factor.
Although this finding is interesting, it is important to keep in mind that the model used in this
study considers the temperature and combustion air to be independent variables. However, in
recovery boilers, the amount of combustion air also affects the char bed temperature.
100
% Volume
10
Na
1
0.1
NaCl
0.01
0.001
KCl
0.0001
0
20
40
60
80
Air Ratio (% Theoretical Air)
100
Figure 4.4 - Na, K and Cl Release from Char Bed as a Function of Combustion Air at 1000C
54
Composition (wt %)
32.3
33.3
31.8
3.8
3.9
3.7
34.3
35.1
33.5
19.5
19.9
19.1
4.9
5.0
4.9
0.8
5.0
5.0
0.2
2.0
2.0
Figures 4.5 and 4.6 indicate the effect of temperature and composition on the Cl and K
enrichment factors. The temperature varied from 800 to 1300C and the combustion air in the
lower furnace was set to 30%. One curve shows the Cl enrichment factor for a black liquor
sample containing 0.8 wt% K and 0.2 wt% Cl. The second curve shows the Cl enrichment factor
for a black liquor sample containing 0.8 wt% K and 2 wt% Cl. The third curve is obtained from a
sample containing 5 wt% K and 2 wt% Cl. The result indicates that, if only the Cl content is
increased, the Cl enrichment factor decreases, but if both K and Cl contents are increased, the Cl
enrichment factor increases. Similar behavior is seen for the K enrichment factor. If both K and
Cl contents are increased, the K enrichment factor increases.
However both enrichment factors are affected by the Cl and K content in the black liquor, the
increases and decreases observed are not significant in both cases. The changes in Cl (from 0.2 to
2 wt%) and K (from 0.8 to 5 wt%) contents in the as-fired black liquor resulted in changes not
bigger than 0.2 in the Cl and K enrichment factors. This result shows that the presence of ash
treatment systems lowering the concentrations of Cl and K in the liquors would not affect
substantially the enrichment factors.
55
Chloride
3.0
EFCl
2.0
1.0
5% K and 2% Cl
0.8% K and 2% Cl
0.8% K and 0.2% Cl
0.0
800
900
1000
1100
Temperature (C)
1200
1300
Potassium
3.0
EFK
2.0
1.0
5% K and 2% Cl
5% K and 0.2% Cl
0.8% K and 0.2% Cl
0.0
800
900
1000
1100
1200
1300
Temperature (C)
Figure 4.6 - Effect of Higher Cl and K Contents on K Enrichment Factor
Combustion Air = 30%, Composition: S/Na2 = 0.35
56
Composition (wt %)
20.4
21.4
5.0
7.4
0.8
0.8
0.2
0.2
Figure 4.7 shows the influence of char bed temperature and sulfur content on Cl and K
enrichment factors. At low temperatures, Cl and K enrichment factors are not affected by the
sulfur content. Although previous works indicated that at low bed temperatures the SO2 present
in the flue gas would lead to the sulfation of the ash reducing Cl enrichment factors, the results in
this work do not show that [43-44]. This happened because the amount of HCl formed by the
sulfation reaction is small compared to the amount of Cl remaining in the ash. Other simulations
were then conducted using ashes with higher Cl content and a similar behavior to the studies
mentioned was observed. In the case of K, the sulfation reaction does not affect its final content
in the ash.
At high temperatures, Cl and K enrichment factors are higher for the liquor with high sulfur
content. This happens because the equilibrium condition in the lower bed changes and the sulfur
salts will remain mostly in the bed [48]. As a result, the liquor with high sulfur content will
produce an ash with higher Cl and K contents, resulting in higher enrichment factors at high
temperatures.
57
Chloride
4.0
EFCl
3.0
S/Na2 = 0.5
2.0
S/Na2 = 0.35
1.0
0.0
800
900
1000
1100
1200
1300
Temperature (C)
Potassium
2.0
S/Na2 = 0.5
1.5
EFK
S/Na2 = 0.35
1.0
0.5
0.0
800
900
1000
1100
1200
Temperature (C)
Figure 4.7 - Effect of Sulfur Content on Cl and K Enrichment Factors
Combustion Air = 30%, Composition: Cl=0.2%, K=0.8%
1300
58
59
3.5
Cl
Enrichment Factor
3
2.5
2
1.5
1
0.5
0
5
7
8
Na Release Amount (wt %)
10
60
the Cl and K enrichment factors for the experiments performed. The comparison between the
experimental and calculated results is shown in Table 4.6.
The results indicate that the model is capable of predicting the enrichment factor with accuracy;
however it is important to highlight that the results are sensitive to the release of the inorganic
chemicals determined experimentally.
Table 4.6 Comparison of Enrichment Factors Determined by EFR Tests and the Model
EFCl
EFK
Experimental
Calculated
Experimental
Calculated
Sample 1
2.11 0.02
2.20
1.58 0.04
1.51
Sample 2
2.89 0.07
2.87
1.10 0.05
1.19
Sample 3
3.71 0.09
3.70
2.03 0.08
2.20
Sample 4
2.54 0.05
2.39
1.60 0.05
1.50
Sample 5
2.32 0.04
2.45
1.87 0.03
1.80
4.4 Summary
There are three important findings which should be highlighted:
1) Cl enrichment factor is more sensitive to changes in the variables studied than the K
enrichment factor. The values calculated for Cl enrichment factor can reach values
exceeding 3.5. On the other hand, K enrichment factor are all in the interval between 1
and 2 for the set of conditions used.
2) Among all parameters studied, the char bed temperature is the most important factor
affecting the Cl and K enrichment factor.
3) The changes in the Cl and K content, in the as-fired black liquor, does not affect the Cl
and K enrichment factors significantly. Therefore, the presence of an ash treatment
system to purge Cl and K from the recovery process would allow the levels of these
elements to be reduced in the process liquors without affecting the enrichment observed
in the precipitator ash.
61
62
solubility, the liquid and solid fraction and the solid composition. The values were then
compared to the ones obtained from OLI and an average error on the training pattern was
calculated. A schematic diagram of the neural network block used to represent the ash treatment
system is shown in Figure 5.1.
63
600
n = 4000
500
R = 0.9991
400
300
300
400
500
600
64
65
due to more advanced monitoring technologies used on its installation while the older plants
have less data for comparison. As described in the methodology, a material balance calculation
was also performed to check the validity of the data and help in finding suitable datasets to be
used in CADSIM. The calculation procedure is shown in Appendix D.
Table 5.1A Input Data Used for Evaporation Plant 1 Simulation
Units
Plant Data
m3/h
%
C
C
kPa
kPa
kPa
kPa
kPa
kPa
kPa
C
%
439.7
14.0
83.5
32.9
-83.6
-70.5
-24.3
186.7
200.0
231.3
232.4
152.9
62.8
Once the plant model in Figure 5.4 reached the steady state, the values available in the mill data
were compared to the model findings. The result is seen in Table 5.1B. As it can be seen, the
result is in good agreement with the data available for evaporation plant 1. A similar procedure
was then adopted for the remaining 4 evaporation plants. The input data for each plant is shown
in the respective table followed by the table with the comparison between the simulation result
and the plant data.
Table 5.1B Comparison of Steady State Data for Evaporation Plant 1
Units
Black Liquor Flow from Intermediate Tank
Steam Economy
Condensate Flow
Surface Condenser Water Flow
Surface Condenser Water Output Temperature
Total Steam Flow
Steam Flow to 1D Effect
Steam Flow to 1C Effect
Steam Flow to 1B Effect
Steam Flow to 1A Effect
Strong Black Liquor Flow to Tank
Strong Black Liquor Temperature to Tank
m3/h
m3/t
m3/h
m3/h
C
t/h
t/h
t/h
t/h
t/h
m3/h
C
200.6
5.2
62.2
2854.8
45.6
69.0
35.9
14.1
10.0
9.1
85.6
119.6
66
Table 5.2A - Input Data Used for Evaporation Plant 2 Simulation
Units
Plant Data
m /h
%
C
C
kPa
kPa
kPa
kPa
kPa
kPa
kPa
kPa
kPa
kPa
C
%
597.3
17.0
86.3
31.8
-80.2
-73.5
-64.7
-50.2
-13.6
73.4
201.6
201.8
211.6
211.8
142.1
63.7
m3/h
m3/t
m3/h
C
t/h
t/h
t/h
t/h
t/h
m3/h
C
254.1
5.8
3659.9
49.2
86.5
35.1
22.6
15.0
13.8
135.2
115.5
213.6
5.4
3644.6
44.5
86.8
37.3
21.4
14.9
13.3
144.7
128.0
Units
Plant Data
m3/h
%
C
kPa
kPa
kPa
kPa
C
%
%
%
%
%
400.2
16.0
87.0
77.7
64.0
45.1
6.6
33.9
66.3
67.6
71.9
70.5
75.8
67
Table 5.3B Comparison of Steady State Data for Evaporation Plant 3
Units
Black Liquor Flow to Intermediate Tank
Black Liquor From Evaporation A+B
Black Liquor Solids to 1D Effect
Steam Economy
Surface Condenser Water Flow
Surface Condenser Water Output Temperature
Steam Flow to 1D Effect
Steam Flow to 1C Effect
Steam Flow to 1B Effect
Steam Flow to 1A Effect
Strong Black Liquor Flow to Tank
Strong Black Liquor Temperature to Tank
m /h
3
m /h
%
3
m /t
3
m /h
C
t/h
t/h
t/h
t/h
3
m /h
C
97.0
240.4
62.6
4.8
3816.3
48.1
21.4
22.0
21.3
21.5
218.3
129.1
105.4
277.7
62.7
4.5
3823.2
42.9
18.2
13.5
13.9
19.4
217.8
126.6
Units
Plant Data
m3/h
%
C
kPa
kPa
kPa
kPa
kPa
kPa
kPa
kPa
kPa
kPa
kPa
C
%
812.5
16.1
88.6
-81.6
-64.2
-52.3
-27.8
8.0
65.3
68.1
239.0
242.1
240.4
240.8
32.0
78.0
68
Table 5.4B Comparison of Steady State Data for Evaporation Plant 4
Units
Black Liquor Solids Effect 1A
Black Liquor Solids Effect 1B
Black Liquor Solids Effect 1C
Black Liquor Solids Effect 1D
Black Liquor Solids Effect 2A
Black Liquor Solids Effect 2B
Black Liquor Solids Effect 3
Black Liquor Solids Effect 4
Black Liquor Solids Effect 5
Black Liquor Solids Effect 6
Black Liquor Solids Effect 7
Vapor Temperature Exit Effect 2A
Vapor Temperature Exit Effect 2B
Vapor Temperature Exit Effect 3
Vapor Temperature Exit Effect 4
Vapor Temperature Exit Effect 5
Vapor Temperature Exit Effect 6
Vapor Temperature Exit Effect 7
Black Liquor Temperature Exit Effect 1A
Black Liquor Temperature Exit Effect 1B
Black Liquor Temperature Exit Effect 1C
Black Liquor Temperature Exit Effect 1D
Black Liquor Temperature Exit Effect 2A
Black Liquor Temperature Exit Effect 2B
Black Liquor Temperature Exit Effect 3
Black Liquor Temperature Exit Effect 4
Black Liquor Temperature Exit Effect 5
Black Liquor Temperature Exit Effect 6
Black Liquor Temperature Exit Effect 7
Temperature of Condensate at Exit Effect 7
Surface Condenser Water Output Temperature
Surface Condenser Water Flow
Total Steam Flow
Strong Black Liquor Flow to Tank
Strong Black Liquor Temperature to Tank
%
%
%
%
%
%
%
%
%
%
%
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
t/h
t/h
m3/h
C
72.3
63.7
61.6
54.1
46.6
43.4
28.1
24.0
21.2
20.3
19.4
114.6
114.1
102.2
91.2
80.7
73.5
54.0
129.1
128.8
128.8
129.9
120.2
111.6
98.1
86.4
76.6
67.1
56.6
58.8
45.7
5440.3
126.4
134.7
134.9
76.5
67
62
55
49.5
36.9
29.6
25.2
22.2
19.9
18.3
120.8
112.5
106.9
101.1
90.4
80.3
56.8
142
141
139
135
125.4
111.7
104.9
93.3
82.5
75.1
60.9
62.5
45.8
5440.3
112.2
140.3
134.7
Units
Plant Data
m3/h
%
C
kPa
kPa
kPa
kPa
kPa
kPa
kPa
kPa
C
474.5
15.6
85.9
-72.9
-62.2
-40.7
-0.2
198.6
205.1
244.4
254.8
28.6
69
Table 5.5B Comparison of Steady State Data for Evaporation Plant 5
Units
Steam Economy
Surface Condenser Water Output Temperature
Total Steam Flow
Steam Flow Effect 1D
Steam Flow Effect 1C
Steam Flow Effect 1B
Steam Flow Effect 1A
Flow of Condensate Exit Effect 7
Vapor Temperature Exit Effect 2A
Vapor Temperature Exit Effect 3
Vapor Temperature Exit Effect 4
Vapor Temperature Exit Effect 5
Vapor Temperature Exit Effect 6
Black Liquor Temperature Exit Effect 1A
Black Liquor Temperature Exit Effect 1B
Black Liquor Temperature Exit Effect 1C
Black Liquor Temperature Exit Effect 1D
Black Liquor Temperature Exit Effect 2A
Black Liquor Temperature Exit Effect 2B
Black Liquor Temperature Exit Effect 3
Black Liquor Temperature Exit Effect 4
Black Liquor Temperature Exit Effect 5
Boiling Point Rise Effect 1A
Boiling Point Rise Effect 1B
Boiling Point Rise Effect 1C
Boiling Point Rise Effect 1D
Boiling Point Rise Effect 2A
Boiling Point Rise Effect 2B
Boiling Point Rise Effect 3
Boiling Point Rise Effect 4
Boiling Point Rise Effect 5
Boiling Point Rise Effect 6
Strong Black Liquor Flow to Tank
Strong Black Liquor Temperature to Tank
m /t
C
t/h
t/h
t/h
t/h
t/h
3
m /h
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
m3/h
C
5.5
47.1
72.9
26.1
22.5
14.1
10.2
348.6
108.4
99.9
86.2
75.4
64.9
142.0
138.3
134.7
129.1
114.4
107.0
87.9
76.7
69.0
20.8
16.6
13.7
9.1
6.0
3.4
2.3
1.7
1.3
1.1
82.7
127.1
In order to help an evaluation of all these data, Figure 5.5 plots the ratio between the mill data
and the respective simulated values for each output variable. All the data of flow rates, pressures,
temperatures and concentrations are shown in this graph. Ratio values close to 1 means that the
simulated values agree well with the actual mill data. As it is seen in Figure 5.5 most data is in
good agreement, except for two groups where the ratio exceeds 1.5 and other 2.0. The first group
represents the steam flow to the evaporators in plant 5 and the other the calculated BPR for some
effects of plant 5. The BPR discrepancies are connected to heat transfer coefficients assumed in
the calculations used by mill personal, while the steam consumption is connected to a fouling
episode. The results suggest that CADSIM is capable of simulating the evaporation plants and
that it ought to be able to simulate the remaining parts of the recovery area.
70
3.0
2.5
2.0
1.5
1.0
0.5
0.0
1
7 10 13 16 19 22 25 28 31 34 37 40 43 46 49 52
Output Variables
Figure 5.5 - Comparison between Simulated and Mill Values for Evaporation Plants
71
Recovery boiler A is a bi-drum boiler with a design firing capacity of 3440 tds/d of black liquor
at 77% dry solids. Air for the liquor combustion is provided in three levels. Under normal
operating conditions, the boiler would be able to achieve 95% reduction efficiency and generate
524 t/h of steam at 6.4 MPa and 450C.
Similarly to the evaporation plants test, the data employed are average values obtained for a three
month period of stable operating condition of the boiler simulated. The input data is presented in
Table 5.6A followed by the comparison between simulation result and boiler data in Table 5.6B.
Recovery boiler B is a single drum boiler that has a capacity of firing 3600 tds/d black liquor at
77% dry solids. The air distribution system is also divided into three levels. The average steam
generation is about 510 t/h of superheated steam at 6.4MPa and 450C. The input data used in
boiler B simulation is given in Table 5.7A and the results of the comparison in Table 5.7B.
Table 5.6A Input Data for Recovery Boiler A Simulation
Streams
Black Liquor
Air
Smelt
Stack gas
Steam
Water
Ash
Items
Units
C
H
O
Na
K
S
Cl
Inerts
Solids Concentration
Flow
Temperature
Higher Heat Value
Ambient temperature
FD air preheat temp.
Excess Air
Smelt reduction efficiency
Temperature
Exit gas temperature
TRS as H2S
SO2
CO
Blowdown flow
Sootblowing steam
Feedwater temperature
Input pressure
Feedwater Temperature
Dust recycle
Cl Enrichment Factor
K Enrichment Factor
SO4/CO3 Ratio
wt%
wt%
wt%
wt%
wt%
wt%
wt%
wt%
wt%
t/d
C
kJ/kg BLS
C
C
% Stoichiometric
%
C
C
ppm
ppm
ppm
of BLS
of BLS
C
MPa
C
% of BLS
Boiler Data
35
3.3
34.1
18.6
2.2
5.5
1.2
0.8
76.6
2980
135
13650
25
117
10
90
860
182
0.2
40
72
3%
9%
110
8.9
130
8
2.7
1.6
25
72
Table 5.6B Comparison of Steady State Data for Recovery Boiler A
Feedwater Flow
Superheater Steam Flow
Boiler Drum Pressure
Superheater Steam Temperature
Superheater Steam Pressure
Sootblower Steam Temperature
Black Liquor Organic Fraction
Primary Air Flow
Secondary Air Flow
Tertiary Air Flow
Sodium in Ash
Potassium in Ash
Chloride in Ash
Carbonate in Ash
Sulfate in Ash
Units
Plant Data
Simulation
t/h
t/h
MPa
C
MPa
C
%
t/h
t/h
t/h
%
%
%
%
%
387.1
369.4
7.1
444.8
6.2
307.1
60.8
130.9
309.5
83.5
28.7
5.5
5.6
1.0
58.7
381.2
369.5
7.1
445.0
6.2
296.1
61.0
132.6
312.3
85.7
29.1
5.8
5.5
1.5
58.1
Air
Smelt
Stack gas
Steam
Water
Ash
Items
Units
C
H
O
Na
K
S
Cl
Inerts
Solids Concentration
Flow
Temperature
Higher Heat Value
Ambient temperature
FD air preheat temp.
Excess Air
Smelt reduction efficiency
Temperature
Exit gas temperature
TRS as H2S
SO2
CO
Blowdown flow
Sootblowing steam
Feedwater temperature
Input pressure
Feedwater Temperature
Dust recycle
Cl Enrichment Factor
K Enrichment Factor
SO4/CO3 Ratio
wt%
wt%
wt%
wt%
wt%
wt%
wt%
wt%
wt%
t/d
C
kJ/kg BLS
C
C
% Stoichiometric
%
C
C
ppm
ppm
ppm
of BLS
of BLS
C
MPa
C
% of BLS
Boiler Data
35
3.3
33.6
18.2
2.5
5.1
2.2
0.8
75.7
2830
133
13980
25
127
10
90
860
170
0.5
74
142
4%
10%
132
8.8
132
8
3.0
1.6
30
73
Table 5.7B Comparison of Steady State Data for Recovery Boiler B
Feedwater Flow
Superheater Steam Flow
Boiler Drum Pressure
Superheater Steam Temperature
Superheater Steam Pressure
Sootblower Steam Temperature
Black Liquor Organic Fraction
Primary Air Flow
Secondary Air Flow
Tertiary Air Flow
Sodium in Ash
Potassium in Ash
Chloride in Ash
Carbonate in Ash
Sulfate in Ash
Units
Plant Data
Simulation
t/h
t/h
MPa
C
MPa
C
%
t/h
t/h
t/h
%
%
%
%
%
378.5
351.5
6.7
429.8
5.9
279.6
60.8
167.8
233.9
94.3
25.8
6.9
13.9
0.8
52.5
380.6
351.3
6.8
429.4
5.9
284.2
61.5
170.6
237.5
97.4
29.3
6.7
13.2
1.0
49.8
Recovery Boiler C is a single drum boiler that processes 2900 tds/d at 77% concentration. The
boiler reduction efficiency is around 94% and generates 433 t/h of steam at 6.4MPa and 455C.
Table 5.8A Input Data for Recovery Boiler C Simulation
Streams
Black Liquor
Air
Smelt
Stack gas
Steam
Water
Ash
Items
Units
C
H
O
Na
K
S
Cl
Inerts
Solids Concentration
Flow
Temperature
Higher Heat Value
Ambient temperature
FD air preheat temp.
Excess Air
Smelt reduction efficiency
Temperature
Exit gas temperature
TRS as H2S
SO2
CO
Blowdown flow
Sootblowing steam
Feedwater temperature
Input pressure
Feedwater Temperature
Dust recycle
Cl Enrichment Factor
K Enrichment Factor
SO4/CO3 Ratio
wt%
wt%
wt%
wt%
wt%
wt%
wt%
wt%
wt%
t/d
C
kJ/kg BLS
C
C
% Stoichiometric
%
C
C
ppm
ppm
ppm
of BLS
of BLS
C
MPa
C
% of BLS
Boiler Data
35
3.3
32.8
19
2.6
5.1
2.1
0.8
76.1
2480
132
13600
25
127
10
92
860
185
0.7
4.2
209
4%
8%
131
9
131
8
3.0
1.5
4
74
Table 5.8B Comparison of Steady State Data for Recovery Boiler C
Feedwater Flow
Blowdown Flow
Boiler Drum Pressure
Superheater Steam Temperature
Superheater Steam Pressure
Sootblower Steam Flow
Black Liquor Organic Fraction
Primary Air Flow
Secondary Air Flow
Tertiary Air Flow
Sodium in Ash
Potassium in Ash
Chloride in Ash
Carbonate in Ash
Sulfate in Ash
Units
Plant Data
Simulation
t/h
t/h
MPa
C
MPa
t/h
%
t/h
t/h
t/h
%
%
%
%
%
328.7
0.5
7.1
435.1
6.1
7.8
60.8
126.3
202.7
58.6
27.9
6.3
7.8
12.3
45.8
331.2
0.52
7.07
436.1
6.19
7.76
60.0
138.4
215.6
69.8
30.4
6.5
6.9
12.3
43.9
Once all the simulations were done, the final collection of data was plotted in Figure 5.7. As seen
in the graph, the agreement between simulated and mill values is excellent. The average error for
all the boilers simulated is around 4% with few variables with an error higher than 10% from the
calculated values.
1.2
1.0
0.8
0.6
0.4
0.2
0.0
1
10 13 16 19 22 25 28 31 34 37 40 43
Output Variables
Figure 5.7 - Comparison between Simulated and Mill Values for Recovery Boilers
75
76
Table 5.9A Input Data Used for Causticizing Plant 1 Simulation
Units
Weak Wash Flow to Dissolving Tank
Raw Green Liquor Density at Tank
Total Alkali Raw Green Liquor
Carbonate in Raw Green Liquor
NaOH in Raw Green Liquor
Sodium Sulfide in Raw Green Liquor
Sulfidity in Raw Green Liquor
Chloride in Smelt
Dregs in Raw Green Liquor
Lime to Slaker
Slaker Temperature
Condensate Flow to Lime Mud Washer
Input Flow to Causticizers
Lime Mud Flow to Filter
Lime Mud Solids to Kiln
Total Fuel to Kiln
m /h
3
kg/m
g(NaOH)/L
g(NaOH)/L
g(NaOH)/L
g(Na2S)/L
%
%
ml/L
t/h
C
3
m /h
3
m /h
3
m /h
%
m3/h
Plant Data
192.2
1139.0
159.9
106.4
3.6
49.0
31.6
4.9
14.4
13.7
99.9
27.8
192.7
68.5
76.9
2645.3
m3/h
g/cm3
C
m3/h
g/L
g/L
g/L
%
g/cm3
kg/m3
m3/h
g(NaOH)/kg
g(NaOH)/L
g(NaOH)/L
%
%
g(NaCl)/L
ml/L
g(K)/L
g(NaOH)/L
g(NaOH)/L
g(NaOH)/L
%
g(CaO)/kg
t/d
%
C
191.4
1.2
83.4
4.9
150.7
130.2
108.2
30.8
1.2
63.7
228.3
156.5
140.6
113.0
36.5
83.0
9.3
0.1
9.4
15.8
55.3
85.3
2.7
940.5
302.4
2.5
260.0
77
Recausticizing plant 2 can produce 8100 m3/d of white liquor with active alkali at about 100g/L
Na2O and 30% sulfidity. The expected causticizing efficiency under steady state operating
conditions would be 82%.
Table 5.10A Input Data Used for Causticizing Plant 2 Simulation
Units
Weak Wash Flow to Dissolving Tank
Raw Green Liquor Density at Tank
Total Alkali Raw Green Liquor
Carbonate in Raw Green Liquor
NaOH in Raw Green Liquor
Sulfide in Raw Green Liquor
Sulfidity in Raw Green Liquor
Chloride in Smelt
Lime to Slaker
Slaker Temperature
Input Flow to Causticizers
Lime Mud Flow to Filter
Lime Mud Solids to Kiln
Total Fuel to Kiln
m /h
3
kg/m
g(NaOH)/L
g(NaOH)/L
g(NaOH)/L
g(Na2S)/L
%
%
t/h
C
m3/h
m3/h
%
m3/h
Plant Data
321.2
1124.1
162.3
106.3
4.3
49.3
29.7
5.3
15.0
103.0
317.0
68.5
76.9
2645.3
m3/h
kg/m3
C
C
m3/h
g(NaOH)/L
g/L
g/L
g/L
%
kg/m3
3
kg/m
3
m /h
g(NaOH)/kg
g(NaOH)/L
g(NaOH)/L
%
%
g(NaCl)/L
ml/L
g(K)/L
g(NaOH)/L
g(NaOH)/L
g(NaOH)/L
%
g(CaO)/kg
t/d
%
C
326.2
1136.3
93.0
89.0
0.9
159.6
132.8
111.8
92.6
30.8
1212.6
63.7
323.0
151.9
133.8
107.1
36.5
79.9
10.0
0.09
6.7
18.1
53.3
80.5
2.7
940.5
504.2
2.5
260
78
The recausticizing plant 3 is designed for 9350 m3 /d of white liquor with a higher active alkali at
105 g/L Na2O and 25% sulfidity. The causticizing efficiency under steady state operating
condition is 83%. The input data for the causticizing plant 3 is shown in Table 5.11A. The
comparison between plant data and simulation results for each of the three areas is shown in
Table 5.11B.
Table 5.11A Input Data Used for Causticizing Plant 3 Simulation
Units
Weak Wash Flow to Dissolving Tank
Raw Green Liquor Density at Tank
Total Alkali Raw Green Liquor
Carbonate in Raw Green Liquor
NaOH in Raw Green Liquor
Sulfide in Raw Green Liquor
Raw Green Liquor Temperature
Chloride in Smelt
Flow Raw Green Liquor to X-Filters
Flow of Dregs from Filters
Lime to Slaker
Slaker Temperature
Input Flow to Causticizers
Lime Mud Flow to Filter
Lime Mud Solids to Kiln
Total Fuel to Kiln
m /h
kg/m3
g(NaOH)/L
g(NaOH)/L
g(NaOH)/L
g(Na2S)/L
C
%
m3/h
m3/h
t/h
C
m3/h
m3/h
%
m3/h
Plant Data
367.5
1164.0
159.7
97.2
3.4
50.7
97.6
5.3
364.5
11.9
23.1
102.6
347.1
132.4
73.4
4181.6
Once all causticizing plant simulations were performed the results were plotted in Figure 5.9. All
parameters of flow, pressure, temperature and concentrations for green and white liquors
measured were compared to the simulated values. The results show only three parameters
presented a ratio over 1.5. The parameter in this case is the concentration of lime mud in the
white liquor. Since this value is usually low, the error may be due to experimental errors in mill
analysis. Also, the standard deviation of the value for this parameter indicates that the simulated
values would not be out of the range seen during normal operating condition. The average error
for all the plants simulated is around 9% with few variables with an error higher than 20% from
the calculated values. Similar to the previous cases, the simulation was also run using average
values over a period of normal mill operation. The agreement is also good in most of the cases.
79
Table 5.11B Comparison of Steady State Data for Causticizing Plant 3
Units
Total flow of Filtered Liquor to Slaker
Green Liquor Density to Slaker
Filtered Green Liquor Temperature
Green Liquor Dregs to Slaker
Dregs in Raw Green Liquor
Total Alkali Filtered Green Liquor
Active Alkali Filtered Green Liquor
Carbonate in Filtered Green Liquor
Effective Alkali in Filtered Green Liquor
NaOH in Filtered Green Liquor
Sulfide in Filtered Green Liquor
Sulfidity in Filtered Green Liquor
Total Alkali at Causticizer 1
Active Alkali at Causticizer 1
Effective Alkali at Causticizer 1
Carbonate in Causticizer 1
NaOH in Causticizer 1
Na2S at Causticizer 1
Temperature at Causticizer 1
White Liquor Total Flow to Storage
White Liquor Total Alkali
White Liquor Active Alkali
White Liquor Effective Alkali
White Liquor Sulfidity
Causticizing Degree
Chloride in White Liquor
Lime Mud in White Liquor
Potassium in White Liquor
Carbonate in White Liquor
Sulfide in White Liquor
NaOH in White Liquor
Residual Carbonate
Lime Availability
Kiln Production
O2 Content in Kiln Flue Gas
Kiln Flue Gas Temperature
m /h
3
kg/m
C
3
m /h
ml/L
g(NaOH)/L
g(NaOH)/L
g(NaCO3)/L
g(NaOH)/L
g(NaOH)/L
g(Na2S)/L
%
g/l
g/l
g/l
g(Na2CO3)/L
g/cm3
kg/m3
C
M3/h
g(NaOH)/kg
g(NaOH)/L
g(NaOH)/L
%
%
g(NaCl)/L
ml/L
G(K)/L
g(NaOH)/L
g(NaOH)/L
g(NaOH)/L
%
g(CaO)/kg
t/d
%
C
368.0
1122.8
93.6
4.9
14
143.2
47.4
95.8
28.5
9.6
37.8
32.0
128.8
108.7
88.7
21.1
1.2
63.7
103.0
320.4
152.2
134.3
106.1
38.5
78.7
4.6
0.1
6.0
17.9
56.5
77.8
3.3
941.8
616.6
5.3
275.0
The results obtained for the simulation of the different parts of the kraft chemical recovery
indicate that CADSIM Plus can be used to calculate Na and S balances for actual mills. The final
step for the validation is now to integrate all collected mill data in a single model that would
simulate the whole process. The chemical balance model will then be used to simulate liquor
compositions and to test the chemical makeup strategies.
80
2.0
1.5
1.0
0.5
0.0
1
9 11 13 15 17 19 21 23 25 27 29 31 33 35
Output Variables
Figure 5.9 - Comparison between Simulated and Mill Values for Causticizing Plants
81
2.0
1.5
1.0
0.5
0.0
1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 85 89 93
Output Variables
Figure 5.10 - Comparison between Simulated Values and Mill Value for Full Mill Simulation
82
not extensively tested in this work, but it may correct the problem allowing simulation of
unstable periods of operation.
Sulfidity (%)
40
39
38
37
Mill Value
36
Calculated Value
35
1
10
Time (days)
Figure 5.11 First Simulation Test of White Liquor Mill Sulfidity
40
Sulfidity (%)
39
38
37
Mill Values
36
Calculated Values
35
1
10
Time (days)
Figure 5.12 Second Simulation Test of White Liquor Mill Sulfidity
The previous result indicated that the model should be tested further. The major focus would be
periods where the sulfidity was significantly altered due to changes in the use of saltcake from
the ClO2 plant. Since the saltcake is composed mostly of sodium sulfate (Na2SO4) and sodium
acidic sulfate (NaHSO4), the mill recycled the effluent to be used as sulfur makeup in the
recovery area to reduce cost and discharge volume.
83
On this test, a maintenance shutdown for a short period of time decreased the recirculation of
makeup from around 80 to 25 kg Na2SO4/ ton of pulp. As a result the sulfidity of the white liquor
to the digester is decreased and then returns to the previous condition once the situation was back
40
160
35
120
30
80
Mill Values
Simulated Values
Saltcake Effluent
25
40
20
Saltcake to Evaporation
(kg Na 2SO 4/adt)
Sulfidity (%AA)
to normal. The result of this simulation with the mill data is presented in Figure 5.13.
0
0
Time (days)
10
15
Figure 5.13 Sulfidity Change Test due to a Short Period Shutdown of ClO2 Plant
It is interesting to notice that the sulfidity levels reduced from around 35% AA to around 30%
AA for the reduction considered, and that the sulfidity started to reduce 3 days after the saltcake
recirculation was reduced. Similarly the duration of the event was three days for the recirculation
and for the sulfidity as well.
84
Fiber Line
The fiber line model included in the Kraft Mill model was developed by Aurel Systems.
The author did not concentrate efforts in validating this part of the model, since a study
conducted by Oliveira and Cardoso [106] showed that the fiber line model in CADSIM is able to
simulate the process in a mill study.
Evaporation Plant
The evaporation plant in the Kraft Mill model was tested with data from the Aracruz mill
as well as data from other mills. This model, while very versatile, does not account for fouling of
the evaporators. If the fouling process has to be considered, a correlation would be needed to
estimate changes in the available heat exchange area over time. Tests conducted by Hajiha [107]
indicated that the model was sensitive to identify important variables in the evaporation process,
given that the data provided was originated from real mill data. However, tests conducted using
random values did not allow the model to reach convergence even after long periods of time.
Recovery Boiler
The recovery boiler in the Kraft Mill model requires a number of specifications due to the
complexity of the process and reactions happening. The specifications include:
Flue Gas CO - Due to incomplete mixing and cool spots in the Recovery Furnace, a small
fraction of the combustion products will be in the form of CO. This is difficult to predict
directly and need to be provided to the model.
Flue Gas Sulfur Fraction - This is the mole fraction of sulfur in the flue gases and need to
be specified.
Fly Ash Loss - This is a weight percent based on total ash mass flow and should be
specified, although losses in the precipitator are small.
Smelt Carbon Fraction - Carbon in the smelt is lumped into the inert component flow.
Generally speaking, this carbon would represent a dead load on the system and it would
not be available to the recovery system when the liquor solids are recirculated to the
boiler.
85
Chloride Enrichment Factor - This value has to be calculated using the EPAC model.
This value indicates the split of NaCl between the liquor and the ash streams. However,
the user has the option to enter the value manually in the Kraft Mill model.
Potassium Enrichment Factor - This value has also to be calculated using the EPAC
model. However, the user can enter the value manually in the model. This value also
indicates the split of potassium between the liquor and the ash streams.
Ratio of Carbone to Sulfate in the Ash - This is the weight ratio of Na2CO3 to Na2SO4 in
the fly ash. This value should be specified in the recovery boiler model.
Incomplete combustion This is flagged in the case where the moles of all the main
elements (i.e. C, H, O, N, Na, K and Cl) are balanced and the moles of O become
negative. In this situation, the moles of carbon and hydrogen are converted to inerts in the
smelt in order to bring the moles of oxygen to 0. When the system is balanced, there will
be a slight excess of oxygen in the flue gases. It is assumed that carbon and hydrogen,
which create the largest demand for oxygen, will become unavailable and end up in the
smelt.
Negative sodium carbonate in the smelt stream: In balancing sulfur and sodium, where
the sulfur content is too high or the overall inorganic solids are out of the correct range,
the residual sodium may be negative. In this situation, the Na2CO3 in the smelt will be
negative and an error message will be issued by the program. This should not occur if the
sulfur moles are not excessive relative to the sodium. This situation can be corrected by
increasing the NaOH flow or by entering Na2CO3 flow or reducing the sulfur flowing in
as SO2.
Causticizing Plant
The causticizing plant model is very sensitive to the lime makeup stream. It is advised
that the changes in the plant should be made in small increments to avoid upsets in the lime mud
filter and causticizers.
86
5.6 Summary
Four important findings are worth mentioning in this chapter:
1) The neural network block was able to calculate the solubilities of different precipitator ash as
done by the OLI software.
2) CADSIM was able to simulate all individual parts of the chemical recovery process as
indicated by the validation results. The discrepancies from the mill values were on average
lower than 10%, but some variables presented differences higher than 20%.
3) The steady state simulation of the full liquor cycle was also successful as expected, once all
individual parts were put together.
4) The dynamic simulation of the full mill was also successful for the two cases presented.
However it is important to mention that only the sulfidity was simulated as a response
parameter over periods of time under very stable operating conditions. Other parameters
were not simulated and unstable operating conditions resulted in poor results.
87
88
100
80
60
40
Cl
20
1%
0
0
30
60
Time (days)
Figure 6.1 Determination of Steady State Condition for Cl and K Ash Concentration
90
89
5
Cl
4
3
2
1
Time to reach steady state
0
0
30
60
90
Time (days)
120
150
Figure 6.2 - Effect of Cl and K Input on Steady State Concentration for Cl=K=1kg/ton pulp
90
10
Cl
8
6
4
2
0
0
30
60
90
Time (days)
120
150
Figure 6.3 - Effect of Cl and K Input on Steady State Concentration for Cl=K=2kg/ton pulp
91
5
Small Inventory (1.5)
4
Large Inventory (3.5)
2
1
0
0
30
60
90
120
Time (days)
Figure 6.4 - Cl Accumulation in Precipitator Ash Effect of Inventory
2
Large Inventory (3.5)
Typical Inventory (2.5)
0
0
30
60
90
120
Time (days)
Figure 6.5 - K Accumulation in Precipitator Ash Effect of Inventory
As expected, an increase in mill soda inventory did not affect the final steady state concentration
of Cl and K, but it requires more time for the system to reach this value. This is understandable
because there are more chemicals stored around the process and thus it takes longer for the
92
concentration to change and to reach a final steady state. The result shown in Figure 6.6 indicates
that the time to reach steady state increases from 32 days for a hypothetical mill with soda
inventory of 1 to 43 days for a small soda inventory mill (1.5), to 65 days for a typical soda
inventory mill and 88 days for a large soda inventory mill. This linear relationship between the
time to reach steady state and the soda volume will be discussed in section 7.1.
100
80
R = 0.9999
60
40
20
0
1
2
3
Soda Inventory Size
Figure 6.6 - Time for Cl and K Concentration to Reach Steady State for Different Inventory
93
As an example of the calculations, the data for 5, 10 and 25% of ash purging and ash treatment
are shown in Figures 6.7 and 6.8. As is seen, the levels of Cl and K reduce as the purging or
portion treated is increased. For Cl, a 5% purging resulted in an ash with 3.66 mol% at steady
state while 10% resulted in 3.29 mol% and 25% purging 2.39 mol%. In the case of K, the
concentrations at steady state for 5% purging is 1.95 mol%, 10% purging resulted in 1.83 mol%
and 25% purging is 1.49 mol%. It is important to notice that the levels of Cl and K at steady state
are close if compared ash purging and ash treatment. This happens because the ash treatment
system efficiency is close to 100%, which is equivalent of the removal by ash purging.
Once the portion being treated or purged is sent back to the process, the levels of Cl and K return
to their original concentrations as expected. Also, as indicated by the dashed lines the time to
reach the steady state condition remains the same.
Figure 6.7 - Accumulation of Cl and K in the Precipitator Ash 5, 10 and 20% Ash Purging
94
Figure 6.8 - Accumulation of Cl and K in the Precipitator Ash 5, 10 and 20% Ash Treated
In order to observe the effects of ash purging and treatment, a graph showing the steady state
levels of Cl and K in the precipitator ash for different portions treated is shown in Figure 6.9.
5
Ash Purged
Ash Treated
4
3
Cl
2
K
1
0
0
20
40
60
80
100
95
The result suggests that above 40% ash purged or treated, the Cl and K contents at steady state
are not significantly reduced. This result is expected since the content of Cl and K in the system
is lower, which makes its removal more difficult. Also the Cl and K inputs to the system are
maintained constant, which prevents the depletion of both ions.
96
40
Makeup Amount (t/d)
0% Ash Purged
30
NaOH
20
ClO2 Effluent
10
Na2SO4 Makeup
0
0
30
60
90
120
Time (days)
150
180
210
Figure 6.10 - Na and S Makeup Requirement to Maintain 29.5% Sulfidity (AA) 33% Ash
Purging
The results for 33% ash treated are shown in Figure 6.11. As is shown, there is a significant
difference between the makeup amounts required in each case. For the purging test, there is a
need to add saltcake makeup. On the other hand, the makeup requirement for the test where the
ash treatment was used, show that the sulfidity could be maintained without saltcake makeup.
97
40
Makeup Amount (t/d)
0% Ash Treated
30
20
NaOH
10
ClO2 Effluent
0
0
30
60
90
120
150
180
210
Time (days)
Figure 6.11 - Na and S Makeup Requirement to Maintain 29.5% Sulfidity (AA) 33% Ash
Treated
As Figures 6.12 and 6.13 indicate, the advantage of ash treatment systems in this case study lies
in the reduced makeup requirement needed to maintain a specified sulfidity. In Figure 6.13, is
seen that all ClO2 effluent available is not enough to sustain the sulfidity as purging increases
above 50%.
98
60
40
NaOH
ClO2 Effluent
20
Na2SO4 Makeup
0
0
20
40
60
80
100
60
40
NaOH
20
ClO2 Effluent
0
0
20
40
60
80
100
99
R8 / SVP Lite
Na3H(SO4)2
5.7 t/d
5.6 t/d
25%
R10 / SVP-SC
Na2SO4
5.8 t/d
8.4 t/d
1%
The results show that the model is able to simulate different ClO2 processes and could be used to
study the impact of by-product streams used as makeup.
6.3 Summary
Regarding the Cl and K balance the following findings summarize the results presented:
1) The input of Cl and K to the mill is directly proportional to the steady state concentration
of these ions in the precipitator ash.
100
2) The soda inventory size does not affect the steady state concentration of Cl and K in the
precipitator ash, but the time for the steady state concentration to be reached. The
increase in soda inventory showed a linear correlation with the time to reach steady state.
3) The ash purging and ash treatment effects on the levels of Cl and K in the precipitator ash
are more pronounced for the first 40% purged or treated, as the fraction of purging or
treatment increase beyond this amount the reduction is not as significant.
With respect to the Na and S balance the findings of the simulations are:
1) For the system studied, the use of ash treatment reduced the Na and S requirement from
128 t/d for 100% ash purging to 52 t/d for 100% ash treatment. The savings with the ash
treatment were able to maintain the recovery cycle at desired sulfidity and alkali stock
without the need of extra makeup stream.
2) The use of R10 ClO2 generator technology allowed a reduction in 24% in effluent
sewered.
101
102
103
To find the general equation that describes this process, a material balance needs to be performed
around the tank. Thus, the rate of change of Cl in the tank, dQ/dt, is equal to the rate at which Cl
is flowing in minus the rate at which Cl is flowing out. The input rate is given by the input
concentration Cin multiplied by the rate f given. The output rate similarly is given by the output
concentration multiplied by the rate f.
Since the output concentration is not given it must be calculated. Considering that the mixture is
well-stirred, the concentration throughout the tank is the same and equal to the output
concentration or more specifically Q(t)/V. Thus the equation governing this process is:
dQ
Qf
C in f
dt
V
(7.1)
where Q is the amount of Cl (for this example is considered kg), t is the unit of time (seconds),
Cin is the input concentration (kg/m3), f is the flow (m3/s) and V is the volume of the tank (m3).
Rearranging this equation it is obtained:
dQ
f
Q VC in
dt
V
(7.2)
dQ
f
dt
Q VC in
V
(7.3)
Integrating the left side of equation 7.3 with respect to Q and the right side with respect to t:
ln Q VC in
ft
K
V
(7.4)
where K is a constant of integration. Now taking the exponential of both sides in equation 7.4:
Q VC in exp( ft / V ) exp( K )
(7.5)
Q VC in k exp( ft / V )
(7.6)
104
It is given that at time zero Q(0), an initial amount Qo is present in the tank, then:
Q 0 VC in k exp( 0 ) k Q 0 VC in
(7.7)
Using the value found for the integration constant k, equation 7.6 becomes:
Q VC in 1 exp ft / V Q 0 exp( ft / V )
(7.8)
Now considering that the concentration at any time is given by C = Q/V and at the beginning by
C0 = Q0/V, equation 7.8 becomes:
C C in 1 e ft / V C 0 e ft / V
(7.9)
Thus it is shown that the concentration at any time inside the tank would be influenced by two
portions: the first portion described by the first term in equation 7.9 is the concentration coming
from the input stream due to the flow process and the second portion described by the second
term is the concentration of the original material that remains inside the tank. A graph
representing the equation 7.9 in the case where the initial concentration is set to zero at time zero
(C0 = 0), Cin = 1kg/m3 and f = 3 m3/day is shown in Figure 7.3.
Concentration (kg/m )
1.5
0.5
0
0
20
40
60
Time (days)
80
100
120
Figure 7.3 Graphic Representation of Equation 7.9 with C0 = 0, Cin = 1kg/m3 and f = 3m3/day
105
As it is shown in Figure 7.3, the curve resembles the values calculated for Cl and K
accumulation in the precipitator ash as seen in the previous chapter. Making the proper unit
conversion and setting the data based on values from Chapter 6, the data obtained from CADSIM
simulations and the data obtained from equation 7.9 have an excellent agreement with
differences not bigger than 1% as indicates Figure 7.4. The time for the system to reach the
steady state concentration as defined in chapter 6 remained at 65 days. Considering that a CSTR
model is being used, it was also calculated the time constant of the process which is
approximately 14 days. This is the time for the concentration to reach 63.2% of its final value
(characteristic of a first order process for t = or 1-e-1).
5
4
Steady State
Concentration
3
2
Time
Constant
Mathematical Formula
0
0
30
60
90
120
150
Time (days)
Figure 7.4 Comparison of CADSIM data for Cl Accumulation Test and Equation 7.9 assuming
C0 = 0, Cin = 4.2kg/m3 and f = 3.5m3/day
It is important to mention that this behavior is verified because the input and output flow rate f
are equal and constant and the input concentration is also constant. However, on a real kraft mill
these values would change over time and an analytical solution such as the one obtained here
would not be possible. In that case, a numerical solution to the concentration problem would be
necessary, which in the case of a kraft mill would be provided by the CADSIM model developed
in this work.
106
(7.10)
C C in
(7.11)
This means that when t , the value of C(t) or C() Cin which physically means that if
enough time is given the mixture originally in the tank will be replaced by the mixture flowing
in, whose concentration is Cin. Furthermore, the concentration at steady state will be directly
proportional to the input concentration provided as the result obtained in section 6.1.2 and shown
in Figure 7.5.
10
Cl = 2kg/ton pulp
8
6
Cl = 1kg/ton pulp
4
2
Time to reach steady state
0
0
30
60
90
Time (days)
120
150
107
At this point it is interesting to provide some insight into the other three parameters present in
equation 7.9, the rate of flow f, the volume of the tank (or system chemical inventory) V and the
initial concentration C0. Similarly to the previous case, if the value of f is increased, the term
exp(ft/V) will tend to zero at a faster pace than originally, which makes the concentration at
steady state C() one that can be reached faster. Physically this indicates that the original
mixture is replaced faster by the one flowing in.
With respect to changes in V, if an increase in the volume of the tank is made, the term exp(ft/V) will tend to zero at a slower pace and therefore it would take more time to reach the steady
state concentration. It is important to consider that in both cases when f or V is changed the
concentration at steady state remains the same equal to Cin and that f and V are linearly
correlated to time as shown in Figures 6.4 to 6.6 in section 6.1.3.
Finally with regard to C0 three situations may occur according to its value being equal, smaller or
larger than Cin. Going back to equation 7.9 and rearranging it:
C C in C 0 C in exp ft / V
(7.12)
If C0 = Cin the concentration in the tank is invariant, since the solution being replaced has the
same concentration and equation 7.12 reduces to:
C C in 0 * exp ft / V C C in
(7.13)
If C0 < Cin, then |C0 Cin| = (C0 Cin) = (Cin C0) therefore:
C C in C in C 0 exp ft / V
(7.14)
Thus, the concentration increases and approaches asymptotically the steady state concentration.
If C0 > Cin, then |C0 Cin| = C0 Cin therefore:
C C in C 0 C in exp ft / V
(7.15)
The concentration in the tank would decrease and approach asymptotically the steady state
concentration. In order to show the effect of initial concentration, an example is shown below for
a tank of 50 m3 containing an initial concentration of salt C0. This tank starts receiving a solution
108
containing 4kg/m3 of salt at time zero. The solution enters and leaves the tank at the rate of 3
m3/day. The impact of initial concentration in the tank is then evaluated by assuming different
initial values (0, 2, 4, 6 and 8 kg/m3). Figure 7.6 shows the results of the calculations.
Concentration (kg/m )
0
0
20
40
60
Time (days)
80
100
120
7.3 Summary
The major findings shown in this chapter were:
1) The data calculated by the CSTR model presented excellent agreement with the data
obtained by CADSIM given all the simplifications in both cases are applicable.
2) The analysis of the variables confirmed the findings of Chapter 6 and gave an insight
in the behavior of the variables studied. As seen, the steady state concentration is
directly influenced by the input concentration as also obtained by CADSIM. This
result suggests that setting the makeup as close as possible to the desired Na2/S ratio
could be helpful to obtain better control over this parameter. The flow rate and the
soda inventory affect the time to reach steady state and as shown these variables are
linearly correlated to the time to reach steady state as expected from the mathematical
model calculations.
109
8. Conclusions
This work focused on the balances of Cl, K, Na and S in the chemical recovery process using a
CADSIM model. Based on the objectives set at the beginning of this document it can be said that
1) The CADSIM model developed was able to simulate processes from a real kraft pulp mill
as demonstrated by the validation process. Furthermore the ash treatment block
developed for the model was able to simulate a real treatment process present in the case
mill used in the validation. The dynamic simulations presented good agreement for the
two cases studied; however tests performed with data from unstable periods of operation
resulted in poor results with the model crashing in most situations.
2) The Na and S balance in the system studied showed that the use of ash treatment reduced
the Na and S requirement from 128 t/d for 100% ash purging to 52 t/d for 100% ash
treatment. The savings with the ash treatment were able to maintain the recovery cycle at
desired sulfidity and alkali stock without the need of extra makeup stream. The use of
R10 ClO2 generator technology allowed a reduction in 24% in effluent sewered.
Furthermore this study also allows the following conclusions:
3) The study on the parameters affecting the Cl and K enrichment factors confirmed that
they are not constant as previously suspected, but the changes are usually small if the
lower bed temperature is not altered. The changes in content of Cl and K in the as-fired
black liquor would not impact extensively the enrichment factors.
4) Regarding the Cl and K balance, the theoretical considerations developed for their
accumulation indicate that the steady state concentration of these ions in the precipitator
ash is directly proportional to the Cl and K input to the mill. The soda inventory affects
the time for the steady state concentration to be reached. The increase in soda inventory
showed a linear correlation with the time to reach steady state. The ash purging and ash
treatment effects on the levels of Cl and K in the precipitator ash are more pronounced
for the first 40% purged or treated; beyond this portion the reductions are small.
110
9. Recommendations
Although the CADSIM program presented very good agreement with the data from the real kraft
mill as shown previously, the result was only true for very stable periods of operation where the
mill was at steady operating condition. Dynamic tests performed under various different
conditions presented in many cases problems with convergence and accuracy. In a few cases the
model crashed due to major discrepancies.
Therefore more studies need to be conducted in order to refine the model capabilities and
provide a more robust program that would be able to simulate a larger number of situations. The
first step should focus on improving the control strategy for the makeup chemicals. Two aspects
should be considered: different input points and different setup controls for the makeup streams.
It is important to highlight that these changes must be performed at slow pace to allow the model
to accommodate the new settings and start converging towards a new steady state. If too many
changes are introduced simultaneously, the discrepancies would build up leading to a crash after
few cycles.
However this process may be very time consuming, the results shown here indicate that these
improvements could make this model even more useful for pulp and paper mills, allowing them
to simulate possible scenarios and plan ahead of time for changes in the process.
111
10. References
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114
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54 Verril, C.L. and Wessel, R.A., Sodium Loss During Black Liquor Drying and
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55 Frederick, W.J., Iisa, K., Wag, K., Reis, V.V., Boonsongsup, L., Forssen, M., Hupa, Sodium
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57 - Frederick, W.J., Hupa, M., Forssen, M., Hyoty, P., Sulfur and Sodium Volatilization During
Black Liquor Pyrolysis, International Chemical Recovery Conference, p. 599-608, 1992.
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1996.
59 McKeough, P, Understanding and Predicting the Release of Sodium, Potassium and
Chlorine during Black Liquor Combustion in the Recovery Furnace, Tappi International
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60 McKeough, P.J., Kurkela, M., Arpiainen, V., Mikkanen, P., Kaupinen, E., Jokiniemi, J.,
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Devolatilization of Fume Formation in Kraft Recovery Furnaces, Journal of Pulp and Paper
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63 Saturnino, D., MASc. Thesis, The Solubility of Kraft Recovery Boiler Precipitator Ash,
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64 - http://www.olisystems.com
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65 Jutila, E., Leiviska, K., The Use of Computer Simulation in the Pulp and Paper Industry,
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70 Wasik, L., Mittet, G.R., Nelson, D.J., Controlling Brownstock Washeing during Production
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73 Bremford, D.J., Mullersteinhagen, H.M., Multiple Effect Evaporator Performance for Black
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76 Galtung, F.L., A Mathematical Model and Digital Computer Based Advanced Control
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77 Costa, A.O.S., Biscaia, E.C., Lima, E.L., Mathematical Description of the Kraft Recovery
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78 Beckwith, W.F., Owen, J.E., Simulation of the Causticizing System of a Kraft Mill, AIChE
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79 Swanda, A.P., Seborg, D.E., Holman, K.L., Sweerus, N., Dynamic Models of the
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80 Edwards, L.L., Singh, P., Lime Kiln Simulation: Impact of Alternative Fuels and Dams,
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119
APPENDICES
120
General Info
This module provides slide shows of all the modules as well as database documentation, answer
to frequently asked questions and a list of useful addresses and references. In addition, the
module also provides information on interfaces that allow access to the FactSage data and
software such as SimuSage for process modeling, OLI Sage Interface to link to OLI aqueous
databank and METSIM for coupled chemical process simulation.
Databases
In FactSage there are two types of thermochemical databases: pure substances databases and
solution databases. The latter contain the optimized parameters for solution phases. The former
contain the properties of stoichiometric compounds, either obtained from phase diagram
optimization or taken from standard compilations. The main databases are:
FTsalt salt database contains data for pure salts and salt solutions formed among
various combinations of cations and anions.
FThall Hall aluminum database contains data for all pure substances and 17
solution phases formed in the system Al-Mg-Na-Li-Ca-F-O.
FThelg aqueous Helgeson database contains infinite dilution properties for 1400
aqueous solute species taken from the GEOPIG-SUPCRT Helgeson public
database including Helgeson equation of state for temperatures up to 350C.
121
Other databases developed for specific uses include alloy databases available upon request:
FScopp (copper alloy database), FSlead (lead alloy database), FSlite (light metal database),
FSstel (steel database) and FSup (ultrapure silicon database) [109].
Calculations
This group of modules is the main part of FactSage. They allow interaction with the databases to
perform calculations to establish thermochemical equilibria and build phase diagrams of systems
in a multitude of formats. The main modules are: Reaction, Predom, EpH, Equilib, OptiSage and
Phase Diagram.
The Reaction module calculates changes in extensive thermochemical properties (H, G, V, S, Cp,
A) for single species, a mixture of species or for a chemical reaction. The Predom module can
calculate and plot isothermal predominance area diagrams for one, two or three-metal systems
using data retrieved form the compound databases. The EpH module is similar to the Predom
module and permits one to generate Eh vs. pH (Pourbaix) diagrams for one, two or three metal
systems from the compound databases.
The Equilib module is the Gibbs energy minimization module in FactSage. It calculates the
concentrations of chemical species when specified elements or compounds react or partially react
to reach a state of chemical equilibrium. The module allows different choice of units, presence of
dormant phases, equilibria constrained with respect to T, P, V, H, S, G or Cp and user-specified
compound and solution data. A variety of calculations modes are also available including phase
targeting, composition targeting, phase transition, open systems with product removal.
The OptiSage module applies the CalPhad approach to generate a consistent set of Gibbs energy
parameters from a given set of experimental data using known Gibbs energy data from wellestablished phases of a chemical system. Finally, the Phase Diagram module permits one to
calculate, plot and edit multicomponent phase diagram sections where the axes can be
combinations of T, P, V, composition, activity, chemical potential, etc.
122
(B.1)
o
123
In the equation (B.1), OLI uses the Helgeson et al framework to obtain the standard state term,
and use the frameworks of Bromley, Zemaitis, Pitzer, Debye-Huckel and others to obtain the
excess term.
The standard state term can be described as:
Mo = M(T,P,, c1,c2,a1,a2,a3,a4)
(B.2)
where , c1,c2,a1,a2,a3,a4 are Helgeson parameters and are specific to each species.
The excess term are connected to the determination of activity coefficients, which describe the
non-ideality of the solution and have the general form of
= DH (I) + BZ (I,T,m)
(B.3)
The term DH is known as the Debye-Huckel expression for long-range electrostatic interactions.
This term describes the activity coefficients of dilute systems:
2
DH i
A zi I 1 2
(B.4)
1 I1 2
where A is the Debye-Huckel coefficient and varies with temperature and solvent properties, zi is
the number of charges of the ions and I is the ionic strength.
The BZ term in equation B.3 is the Bromley-Zemaitis expression for short-range interactions:
2
C
I
D
I
m (B.5)
ij
ij
ij
j
2 1 1.5I / zi z j 2
j 1
NO
where NO is the number of ions with opposite charges to i, Bij, Cij, Dij are empirical
temperature-dependent parameters for cation-anion interactions and mj is the molality of the
species j.
For other interactions such as ion-molecule and molecule-molecule, OLI uses other models.
124
125
The liquor concentration and also the steam conditions change through the plant. This
influences the characteristics of the liquor so that each effect must be calculated with
different parameters.
The boiling point rise has a considerable influence on the heat transfer, since it defines
the available effective temperature difference.
In a multiple effect plant, the total temperature difference is split between the effects
according to various parameters.
The calculation employed for most simulators including CADSIM is iterative by its
nature. It is extremely elaborate to make manually especially when trying for high
precision. An easier way to explain the calculations is using a spreadsheet approach.
The following gives a typical sequence for the calculations in an evaporation plant.
Given parameters:
Dry solids flow;
Number of stages;
Specific Heat;
126
Define the effective temperature difference in all the stages:
The live steam saturation temperature and the cooling water outlet temperature define the
total temperature difference.
Pressure and temperature differences due to piping losses are defined if available. Most
important are to define the pressure loss of live steam before the first effect and the temperature
difference in the surface condenser.
When the effective temperature difference is defined, this is distributed to the different stages
with the method described in detail below.
Prepare the heat balance for each stage:
The main heat flow is in the steam or vapor transferred from one effect to another. The concepts
used in the evaporation calculations have the following definitions:
Total temperature difference = Total t = live steam saturation temperature of the heating
element of the first effect minus condensing temperature in the surface condenser.
Total effective temperature difference = t = total thermal driving force. It is calculated as the
total t minus sum of boiling point rises minus sum of temperature drops due to pressure losses.
The total effective t for multiple effect evaporation is the sum of the effective t of the effects:
t = t1 + t2+.+tn
For each effect, the general heat transfer formula is valid:
Q = U x A x t
or t = Q / (U x A)
For the evaporator train, the equations for each effect would be:
t1 = Q1 / (U1 x A1), t2 = Q2 / (U2 x A2), t3 = Q3 / (U3 x A3), tn = Qn / (Un x An)
To solve this equation group, the relations between the effects are formed by dividing the
equations so that all are expressed as function of t1:
t2 = t1 x (Q2 x A1 x U1) / (Q1 x U2 x A2), t3 = t1 x (Q3 x A1 x U1) / (Q1 x U3 x A3)
The effective temperature difference for effect 1 can then be recalculated:
t 1
t
Q 2 x A1x U1 Q 3 x A1x U1
Q x A1 x U 1
1
..... n
Q1 x A n x U n
Q1 x A 2 x U 2 Q1 x A 3 x U 3
127
When t1 has been determined, the temperature difference for the other effects can be calculated
with the formulas for each t.
mVi hVi + mCi CpWi tCi + mLi CpLi tLi = mVo hVo + mCo CpWo tCo + mLo CpLo tLo
An Excel spreadsheet shows the calculation for three-stage evaporation. The basic design data
are indicated below. The calculation starts by assuming the evaporation in the first stage. This
then determines the heat energy available in the following effects. The characteristics of the
liquor and vapor are calculated for each stage. A flashing of the condensate from effects 2 and 3
has been considered. This is a simplified calculation. It does not consider internal pressure losses
between the effects or the losses of non-condensable gases that vent from the evaporation.
ASSUMPTION
It is necessary to assume for the first iteration
that the evaporation in each body is equal and
that the effective t is the same in each body.
CALCULATION
Once the new t is calculated it is inserted in
the respective places (D46, D47 and D48) and
the new evaporation either (D16 and D17), the
procedure is repeated until convergence.
128
SIMPLIFIED EVAPORATOR CALCULATION
Basic Design Data
Unit
Value
Formula
Number of Effects
3 Input Value
Effect 3 -> Effect 2 ->
Liquor Flow Pattern
Effect1
Black Liquor Inlet Concentration
0.2 Input Value
Black Liquor Outlet Concentration
0.5 Input Value
Black Liquor Inlet Temp. Effect 3
C
70 Input Value
Evaporation Capacity
kg/s
30 Input Value
Live Steam Saturation Temp. to Effect 1
C
120 Input Value
Saturated Vapor Temp. out Effect 3
C
60 Input Value
Dry Solids Calculation
Dry Solids Flow
kg/s
10 D9/(1/D6-1/D7)
Evaporation
Effect 1
kg/s
10 Input Value
Effect 2
kg/s
9.56 Input Value
Effect 3
kg/s
10.37 Input Value
Total Evaporation
kg/s
30 SUM(D15:D17)
Liquors Flow
Effect 1 out
kg/s
20 D13/D7
Effect 2 out
kg/s
30 D20+D15
Effect 3 out
kg/s
39.56 D21+D16
Effect 3 in
kg/s
49.93 D22+D17
Liquor Concentrations
Effect 1 out
0.5 D13/D20
Effect 2 out
0.333333 D13/D21
Effect 3 out
0.252781 D13/D22
Effect 3 in
0.20028 D13/D23
Boiling Point Rise
Effect 1
C
8.628671
Effect 2
C
4.256696
Effect 3
C
2.702241
Liquor Temperatures
Effect 1 out
C
105.6 D10-D46
Effect 2 out
C
81.91133 D52-D47
Effect 3 out
C
62.72463 D53-D48
Effect 3 in
70 Input Value
Heat Transfer Coefficient
Effect 1
kW/m2C
1.2 Input Value
Effect 2
kW/m2C
1.6 Input Value
Effect 3
kW/m2C
2 Input Value
Boiling Point Rise Calculation
BPR = 6.173*D25-7.48*D25*(D25)^.5+32.747*(D25)^2
BPR = 6.173*D26-7.48*D26*(D26)^.5+32.747*(D26)^2
BPR = 6.173*D27-7.48*D27*(D27)^.5+32.747*(D27)^2
129
SIMPLIFIED EVAPORATOR CALCULATION
Effective t Calculation
C
60 D10-D11
Total available t
Sum of BPR
C
15.58761 D30+D31+D32
C
44.41239 D43-D44
Total Effective t
C
14.4 D45/3
Effective t, Effect 1
C
15.06 D45/3
Effective t, Effect 2
C
14.93 D45/3
Effective t, Effect 3
Check Sum
44.39 SUM(D46:D48)
Vapor Saturation
Temperatures
Live Steam Saturation
C
120 Input Value
Effect 1
C
96.97133 D34-D30
Effect 2
C
77.65463 D35-D31
Effect 3
C
60.02239 D36-D32
Vapor Enthalpy
Live Steam
kJ/kg
2704 Input Value
Effect 1
kJ/kg
2661 Input Value
Effect 2
kJ/kg
2631 Input Value
Effect 3
kJ/kg
2609 Input Value
Condensate Enthalpy
Live Steam
kJ/kg
503 Input Value
Effect 1
kJ/kg
384 Input Value
Effect 2
kJ/kg
307 Input Value
Effect 3
kJ/kg
251 Input Value
Liquor Specific Heat
Effect 1
kJ/kg, C
3.292643 Cp1
Effect 2
kJ/kg, C
3.539172 Cp2
Effect 3
kJ/kg, C
3.669803 Cp3
Inlet Liquor
kJ/kg, C
3.775786 Cp4
Energy in Liquor
Effect 1 out
kJ/s
6954.062 D20*D34*D67
Effect 2 out
kJ/s
8696.949 D21*D35*D68
Effect 3 out
kJ/s
9106.199 D22*D36*D69
Inlet Liquor
kJ/s
13196.75 D23*D37*D70
Energy Demand
Effect 1
kJ/s
24867.11 D15*D58+D72-D73
Effect 2
kJ/s
24114.47 (D15+D89)*(D58-D63)
Effect 3
kJ/s
22477.62 (D82+D90)*(D59-D64)
New Evaporation
Effect 1
kg/s
10 D15
Effect 2
kg/s
9.321066 (D78+D74-D73)/D59
Effect 3
kg/s
10.18328 (D79+D75-D74)/D60
Vapor Production /
Demand
Effect 1
kg/s
11.2981 D77/(D57-D62)
Effect 1 to Effect 2
kg/s
10.59046 D81+D89
Effect 2 to Effect 3
kg/s
9.671954 D82+D90
Cp1 = 4.216*(1-D25)+(1.675+(3.31*D34)/1000)*D25+(4.87-20*D34/1000)*(1-D25)*(D25)^3
Cp2 = 4.216*(1-D26)+(1.675+(3.31*D35)/1000)*D26+(4.87-20*D35/1000)*(1-D26)*(D26)^3
Cp3 = 4.216*(1-D27)+(1.675+(3.31*D36)/1000)*D27+(4.87-20*D36/1000)*(1-D27)*(D27)^3
Cp4 = 4.216*(1-D28)+(1.675+(3.31*D8)/1000)*D28+(4.87-20*D8/1000)*(1-D28)*(D28)^3
130
SIMPLIFIED EVAPORATOR CALCULATION
Condensate Flash
Effect 1 to Effect 2
kg/s
0.590458 D85*(D62-D63)/(D58-D63)
Effect 2 to Effect 3
kg/s
0.350889 D86*(D63-D64)/(D59-D64)
Heat Transfer Area
Effect 1
m2
1040 Input Value
Effect 2
m2
1040 Input Value
Effect 3
m2
1040 Input Value
Heat Transfer Capacity
Effect 1
kJ/s
17971.2 D39*D46*D92
Effect 2
kJ/s
25059.84 D40*D47*D93
Effect 3
kJ/s
31054.4 D41*D48*D94
New t
Effective t, Effect 1
23.94307
Effective t, Effect 2
Effective t, Effect 3
Check Sum
C
C
12.00343
8.46589
44.41239
D45/(1+(D83*D97*D39)/(D82*D98*D40)
+(D84*D97*D39)/(D82*D99*D41))
D100*(D82*D96*D39)/(D81*D97*D40)
D100*(D83*D96*D39)/(D81*D98*D41)
SUM(D100:D102)
131
(1)
The other reactions involve the inorganic portion of the black liquor and require individual
evaluation for the material balance to be properly addressed. They can be represented by the
general reaction as shown in equation 2 and contains the main components of the smelt stream
leaving the bottom of the recovery boiler:
Inorganic Matter (C, O, Na, S, K, Cl) + O2 Na2S + Na2SO4+ NaCl + Na2CO3 + K2CO3 (2)
132
C
H
O
Na
K
S
Cl
Si, Al, etc
Sol
HHV (kJ/kg BLS)
NHV (kJ/kg BLS)
133
Na
S
O
Cl
Si, Al, etc
wt%
32.40%
22.40%
44.80%
0.30%
0.10%
Based on data available in Tables E.1 to E.3, the material and energy balance calculation will be
performed for a Kraft recovery boiler using an Excel spreadsheet.
Table E.3 Sample Operating Parameters for a kraft recovery boiler
Air
Black
liquor
Smelt
Stack
gas
Stream
Circuit
Item
Excess forced draft air
Infiltration air
Total excess air
Ambient temperature
Humidity in air
FD air preheat temp.
Concentration Solids
Temperature
Salt cake makeup
Direct heating liquor
Dust recycle
Smelt reduction eff.
Organic C in smelt
Temperature
Enthalpy
Exit gas temperature
TRS as H2S
SO2
CO
H2
Particulate
Na2SO4 particulate
Na2CO3 particulate
K2SO4 particulate
K2CO3 particulate
NaCl particulate
Na % in particulate
S % in particulate
Blowdown flow
Sootblowing steam
Feed water temp.
Steam temperature
Steam pressure
Enthalpy of steam
6%
9%
15%
27
0.013
150
70%
108
3%
1.7%
10%
90%
1%
850
1350
210
15
75
200
200
0.1
80%
8%
7.3%
0.7%
4%
31%
19.4%
11%
18%
110
482
62.25
3372
Units
Stoichiometric
Stoichiometric
Stoichiometric
C
kg H2O/kg dry air
C
C
wt. of BLS
wt. of wet BL
wt. of initial Na
wt. of smelt
C
kJ/kg
C
ppmv dry flue gas
ppmv dry flue gas
ppmv dry flue gas
ppmv dry flue gas
g/DSCM
wt as Na2SO4
wt as Na2CO3
wt as K2SO4
wt as K2CO3
wt as NaCl
of BLS
of BLS
C
C
Bar
kJ/kg
134
Material Balance
In order to calculate the material balance, it will be assumed that complete combustion takes
place and minor losses are ignored. Thus, the first step is to consider the input as 100 kg of black
liquor dry solids. Since the heavy black liquor injected in the boiler has a 70% dry solids content
the total input to the boiler can be obtained by:
Black Liquor Input = (100*100)/70 = 142.86 kg
From Table E.3 it is also known that the saltcake makeup is 3% of the black liquor solids flow,
which gives an input of 3 kg. Therefore, at this point two streams are already identified for the
material balance as shown in Figure E.2.
46 g + 32 g = 78 g
(3)
135
Therefore the amount of Na2S can be calculated multiplying the total amount of black liquor
solids entering the boiler (100 kg) by the amount of sulfur content in the liquor (4%) and the
smelt reduction efficiency of the boiler (90%). The smelt reduction efficiency indicates how
much of the sulfur exits the boiler in the reduced form, or in other words as Na2S. This
calculation gives the output of sulfur, but not Na2S. But by the equation above and the respective
molecular weights of S and Na2S, it is indicated that each 32g of S will generated 78g of Na2S,
since Na is in excess in the boiler. Thus the amount of Na2S from the BLS is
Na2S from BLS = 100 * 0.04 * 0.9 * (78/32) = 8.78 kg/100kg BLS
Since the makeup also contains Na and S, part of the Na2S can be generated by reactions in the
boiler, thus to account for the makeup the calculation would include the rate of makeup input
that is 3% and the sulfur content in the makeup (22.4%) calculation becomes:
Na2S from makeup = 100 * 0.224 * 0.9 * 0.03* (78/32) = 1.47 kg/100kg BLS
Finally the total amount of Na2S is the sum of both amounts that is:
Na2S total = 10.25 kg/100kg BLS
The second chemical is Na2SO4 and it results from an incomplete reduction of the sulfur in the
boiler. Similarly a simplified equation to its generation is given by equation 4:
2Na + S + 2O2 Na2SO4
Molecular Weights
(4)
The amount of Na2SO4 can be calculated similarly to the previous situation, however considering
not the reduction efficiency, but the remaining sulfur (100-90% or 10%). Once obtained the
sulfur not reduced from the BLS the amount of Na2SO4 is calculated considering that 32g of S
can produce 142 g of Na2SO4. This will give:
Na2SO4 from BLS = 100 * 0.04 * (1-0.9) * (142/32) = 1.78 kg/100kg BLS
Considering the portion that comes from the makeup as in the previous situation, the calculation
will be:
Na2SO4 from makeup = 100 * 0.224 * (1-0.9) * 0.03* (142/32) = 0.30 kg/100kg BLS
136
Therefore the total amount of Na2SO4 is given by the sum of both:
Na2SO4 = 2.08 kg/100kg of BLS
The next chemical considered in the equation 2 is NaCl. Similarly to the previous cases part of it
is generated from the BLS and part from the makeup chemicals. Considering the BLS the
calculation, equation 5 accounts for NaCl generation:
Na + Cl NaCl
Molecular Weights
(5)
Then the amount of NaCl is obtained by multiplying the black liquor solids input (100 kg) by the
content of Cl (0.6%) and the proportion of Cl per each NaCl generated (58.5/35.5), then
NaCl from BLS = 100 * 0.006 * (58.5/35.5) = 0.99 kg/100kg BLS
To calculate the amount inserted with the makeup it is considered in the calculation the makeup
amount and the content of Cl in it (0.3%):
NaCl from makeup = 100 * 0.003 * 0.03 * (58.5/35.5) = 0.01 kg/100kg BLS
And the total amount is again the sum of both amounts:
NaCl total = 1.00 kg/100kg of BLS
The next chemical is Na2CO3. Based on measurements the remaining Na available in the smelt
consists of this chemical. In order to obtain the amount of Na2CO3 it is necessary to consider the
equation 6:
4Na + 2C + 3O2 2Na2CO3 (6)
Molecular Weights
Thus the total amount of Na2CO3 is obtained by subtracting the total amount of Na minus the
amounts contained in the other chemicals already calculated. The total amount is given by the
flow of black liquor solids (100 kg) multiplied by the Na content in the BLS (19.7%) minus the
amounts with Na2S, Na2SO4 given by the sulfur content multiplied by the (46/32) proportion and
NaCl given by the chloride content multiplied by the (23/35.5) proportion. Thus
137
Remaining Na = (100) * (0.197 (46/32) * 0.04 (23/35.5) * 0.006)
This calculation will provide the amount of sodium not of sodium carbonate. To obtain the
sodium carbonate we must consider the equation 6, where each 46g of sodium generates 106 g of
sodium carbonate, then:
Na2CO3 = (100) * (0.197 (46/32) * 0.04 (23/35.5) * 0.006) * (106/46) = 31.25 kg/100kg BLS
The last chemical in the equation 2 is K2CO3 and the amount in the smelt is obtained by the
content of K in the black liquor dry solids. Therefore the calculation is done by multiplying the
total black liquor dry solids flow (100 kg) by the potassium content (1.6%) and the equation 7 for
potassium carbonate generation:
4K + 2C + 3O2 2K2CO3
Molecular Weights
(7)
138
139
Now based on the amounts of chemicals generated by the organic and inorganic reactions in the
recovery boiler, it is possible to estimate the stoichiometric oxygen requirement for the boiler.
This is done based on the equations 1 through 7 given above. Thus the oxygen needed for
sodium sulfate generation is calculated by multiplying the amount of Na2SO4 formed (2.08 kg)
by the amount of oxygen needed according to the equation 4 (64/142). Similar calculation is used
for the other chemicals (Na2CO3, K2CO3, CO2 and H2O):
O2 needed for Na2SO4 formation = 2.08 * (64/142) = 0.93 kg/100kg BLS
O2 needed for Na2CO3 formation = 31.25 * (48/106) = 14.15 kg/100kg BLS
O2 needed for K2CO3 formation = 2.83 * (48/138.2) = 0.98 kg/100kg BLS
O2 needed for CO2 formation = 114.46 * (32/44) = 83.24 kg/100kg BLS
O2 needed for H2O formation = 29.70 * (16/18) = 26.40 kg/100kg BLS
Once all the oxygen needed is obtained the total required is the sum of all individual reactions:
Total O2 required = 0.93 + 14.15 + 0.98 + 83.24 + 26.40 = 125.7 kg/100kg BLS
In order to calculate the total air flow necessary it is important to consider that some oxygen
enters with the black liquor as well as with the makeup chemicals. Thus this amount has to be
calculated. To do that it is multiplied the flow of BLS (100 kg) by the oxygen content in the BLS
(35.7%) and added with the amount of makeup flow multiplied by the oxygen content in the
makeup. Thus the calculation is:
Oxygen in BLS and Makeup = 100 * 0.357 + 100 * 0.03 * 0.448 = 37.04 kg/100kg BLS
Considering the amount in the BLS and makeup are already fed to the boiler, the remaining
oxygen required need to be supplied by the combustion air stream. This is given by:
Oxygen required from Air = 125.7 37.04 = 88.66 kg/100kg BLS
Assuming that the composition of the air is 23.2% of O2 and 76.8% of N2, the stoichiometric
amount of air need can be obtained by:
Stoichiometric Amount of Air = 88.66/0.232 = 382.16 kg/100kg BLS
Nitrogen in combustion Air = 382.16 * 0.768 = 293.53 kg/100kg BLS
140
To identify the amount of air admitted to the boiler, it is important to consider that the required
combustion air is driven to the interior of the boiler by induced draft fans to provide the
temperature and amount needed during different operating conditions of the boiler. At normal
operating conditions the system provides an amount of air in excess of 6% of the stoichiometric
amount. Thus the total forced draft air is:
Excess air = 382.16 * 0.06 = 22.93 kg/100kg BLS
Total Forced Draft Air = 382.16 + 22.93 = 405.09 kg/100kg BLS
Finally it is necessary to consider that an equipment of the size of a recovery boiler has
numerous leaks that permit a significant amount of air to infiltrate in the boiler. Most boiler
manufacturers agree that this number varies greatly, but an acceptable estimate would be around
9% of the stoichiometric air. Thus the infiltration air is:
Infiltration air = 382.16 * 0.09 = 34.40 kg/100kg BLS
Total Excess Air = 22.93 + 34.40 = 57.33 kg/100kg BLS
This will lead to the total air flow that is:
Total Air Flow = 382.16 + 57.33 = 439.49 kg/100kg BLS
Figure E.4 contains the calculations done till now. The last stream to be calculated to complete
the material balance is the flue gas that is generated by the recovery boiler. To calculate that
stream it is necessary to consider some other information. Some water enters with the black
liquor, since the heavy liquor contains 70% dry solids, being the remaining amount water. This
water will come out with the flue gases. Also the air that enters the boiler has some humidity that
has to be accounted for the flue gas stream. Finally part of the steam generated in the boiler is
used in devices called sootblowers to keep the surfaces of the heat exchange tubes in the upper
boiler clean. The steam used will end up as part of the flue gases.
Thus considering the water entering with the black liquor, the steam in stack will calculated
considering the amount of black liquor dry solids (100 kg) multiplied by the water content (30%)
divided by the dry solid concentration (70%), giving:
Steam from black liquor = 100 * (1-0.7) / 0.7 = 42.86 kg/100kg BLS
141
For the humidity of air, it is given an estimate of 0.013 kg of H2O per kg of dry air, which would
result in an amount of water equal to:
Humidity in Air = 439.49 * 0.013 = 5.71 kg/100kg BLS
142
143
Sensible Heat in Black Liquor = (1/0.7) * 2.65 * (108-25) = 314 kJ/kg
The air also contains sensible heat and it is calculated similarly, considering the total flow of air
calculated previously and a heat capacity of 1.006 kJ/kg*C, thus:
Sensible heat in Air = (439.49/100) * 1.006 * (27-25) 9 kJ/kg
The forced draft air in most recovery boilers is preheated before entering the combustion
chamber, which makes necessary to consider this condition in the energy balance. This
calculation is similarly to the previous one just considering only the forced draft air and a new
temperature difference, which results:
Heat to preheat air = (405.09/100) * 1.006 * (150-27) = 501 kJ/kg
The next streams to be considered are the sootblower that is used to remove deposits that may
build up in the tube banks in the heat exchange area. The sootblower uses steam that comes from
the feedwater for the boiler. The amount of heat in the feedwater for the sootblowers is
calculated multiplying the flow of sootblowing steam (18 kg/100kg BLS) by the heat capacity of
water (4.19 kJ/kg*C) and the temperature difference.
Heat in the feedwater for sootblowing steam = (18/100) * 4.19 * (110-25) = 64 kJ/kg
Finally it is necessary the blowdown stream that is the amount of low pressure steam that is
distributed to the mill for different purposes. The calculation is similar to the previous one since
the flow of blowdown is already known (11% of BLS flow)
Heat in the feedwater for blowdown = 0.11 * 4.19 * (110-25) = 39 kJ/kg
Once all input heat is obtained the total input heat is obtained by adding the all the input values:
Total Heat Input = 13950 + 314 + 9 + 501 + 64 + 39 = 14878 kJ/kg of BLS
To complete the energy balance the heat output from all streams as well as the energy consumed
by the chemical reactions has to be considered. Thus to start the sensible heat that is lost with the
dry flue gas should be calculated. It is done by considering the total amount of dry flue gas (CO2
+ N2 + O2) and a heat capacity of the mixture equal to 1.02 kJ/kg.
Sensible Heat in Flue Gas (dry) = (114.46 + 439.49)/100 * 1.02 * (210-25) = 1045 kJ/kg
144
Since in the combustion process water vapor is generated the calculation must to be done
separately since the heat capacity of the water is bigger than the dry flue gas. In this case it will
be considered the heat capacity constituted of one term regarding the latent heat of vaporization
(2770 kJ/kg*C) and a steam heat capacity of 1.98 kJ/kg*C at a reference temperature of 200C.
Then the calculation for the heat loss from the water generated during the combustion is:
Heat loss from water formed = (29.70/100) * (2770 + 1.98 * (210-200)) = 829 kJ/kg
Other source of heat loss is the water that enters with the black liquor solids, since its content is
70%, being the remaining water. Therefore the heat loss with the steam from evaporating this
water is given by:
Heat loss from water in the black liquor = ((1/0.7) 1) * (2770 + 1.98 * (210-200)) = 1196 kJ/kg
Considering now the smelt stream, it is necessary to find the heat loss with the fused salts leaving
the boiler. Considering the given enthalpy of smelt the calculation becomes:
Sensible heat in smelt = (47.51/100) * 1350 = 641 kJ/kg
The most important chemical reaction that consumes energy in the recovery boiler is the
reduction of the sulfur compounds to sodium sulfide (Na2S). This reaction consumes 12900
kJ/kg for the average boiler conditions. Considering the amount of Na2S formed the heat
consumed can be estimated by:
Heat to form sulfide = (10.25/100) * 12900 = 1322 kJ/kg
Another source of heat loss is the steam leaving the boiler from the sootblower use and the
blowdown. They are calculated similarly to the previous equations:
Heat loss from Sootblowing = (18/100) * (2770+ 1.98 * (210-200)) = 502 kJ/kg
Heat Loss from Blowdown = 0.11 * 1150 (blowdown enthalpy) = 127 kJ/kg
Finally it is necessary to consider radiation losses from the boiler and other minor losses due to
leaks and minor streams. A rule of thumb for these numbers according to many boiler
manufacturers is to consider the radiation losses equal to 0.3% of the total heat input and the
145
unaccounted minor losses as 2% of the total heat input. Considering the numbers already
obtained, it is possible to calculate:
Heat losses from radiation = 0.003 * 14878 = 45 kJ/kg
Heat losses from unaccounted minor streams = 0.02 * 14878 = 298 kJ/kg
The total heat loss is then the sum of all individual losses:
Total heat loss = 1045 + 829 + 1196 + 641 + 1322 + 502 + 127 + 45 + 298 = 6005 kJ/kg
The heat available to steam generation is then the difference between the heat input and the heat
losses:
Heat to Steam = 14878 6005 = 8873 kJ/kg
This amount of energy will represent a thermal efficiency of:
Thermal Efficiency = (8873/14878) * 100 60%
Finally it would be possible to identify the amount of steam generated per kilogram of black
liquor solids burned. Considering the given enthalpy of the final steam product (3372 kJ/kg), the
data for the feedwater and the energy available for steam generation an estimate of the steam
production can be made. To calculate that it is considered the energy available for steam
generation and divide this amount by the energy increase in the steam considering the final
enthalpy minus the enthalpy of the feedwater and the latent heat of vaporization. Then:
Steam for the mill = 8873 / (3372 104.8 4.19 * (110-25)) = 3.05 kg steam/kg BLS
Based on literature data from boiler manufacturers, the amount of steam generated per kilogram
of BLS burned usually is between 3 to 3.5 depending on specific operating conditions and black
liquor heating value. The total amount of feedwater would be the sum of the steam for the mill
and sootblowing steam and the blowdown water, thus:
Feedwater to boiler = 3.05 + 0.18 + 0.11 = 3.34 kg of water/kg BLS
Based on the data obtained it is possible to see that improvements in the efficiency of the boiler
can be achieved if the flue gas temperature at the exit of the boiler could be lowered by using the
flue gas to exchange heat with other points in the boiler. Another important factor would be to
146
increase the solids content in the black liquor prior entering the boiler. Also to increase the
efficiency of the sootblower devices would lead to minor losses of steam that could be used in
other areas.
B
4
5
6
7
8
9
10
11
12
13
14
15
16
17
Element
Carbon
Hydrogen
Oxygen
Sodium
Potassium
Sulfur
Chloride
Inerts
Solids
Higher Heat
Net Heat V.
Ass. Red.
O
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
C
D
E
J
K
INPUT DATA - BLACK LIQUOR PROPERTIES
C
H
O
Na
K
S
Cl
Si, Al, etc
Sol
HHV
NHV
wt% BLS
35%
3.30%
35.70%
19.70%
1.60%
4%
0.60%
0.10%
70%
13950
12093
90%
Element
Sodium
Sulfur
Oxygen
Chloride
Inert
Na
S
O
Cl
Si, Al, etc
kJ/kg BLS
kJ/kg BLS
Black
Liquor
Smelt
Stack
Gas
Item
Excess forced draft air
Infiltration air
Total excess air
Ambient temperature
Humidity in air
FD air preheat temp.
Concentration Solids
Temperature
Saltcake makeup
Direct heating liquor
Dust recycle
Smelt reduction eff.
Organic C in smelt
Temperature
Enthalpy
Exit gas temperature
TRS as H2S
SO2
CO
H2
Particulate
Na2SO4 particulate
Na2CO3 particulate
K2SO4 particulate
K2CO3 particulate
NaCl particulate
Na % in particulate
S % in particulate
6%
9%
15%
27
0.013
150
70%
108
3%
1.7%
10%
90%
1%
850
1350
210
15
75
200
200
0.1
80%
8%
7.3%
0.7%
4%
31%
19.4%
Units
Stoichiometric
Stoichiometric
Stoichiometric
C
kg H2O/kg dry air
C
C
wt. of BLS
wt. of wet BL
wt. of initial Na
wt. of smelt
C
kJ/kg
C
ppmv dry flue gas
ppmv dry flue gas
ppmv dry flue gas
ppmv dry flue gas
g/DSCM
wt as Na2SO4
wt as Na2CO3
wt as K2SO4
wt as K2CO3
wt as NaCl
L
wt%
32.40%
22.40%
44.80%
0.30%
0.10%
147
34
35
36
37
38
39
40
Stream
Circuit
W
4
5
6
Blowdown flow
Sootblowing steam
Feedwater temp.
Steam temperature
Steam pressure
Enthalpy of steam
Reference temp.
11%
18%
110
482
62.25
3372
25
of BLS
of BLS
C
C
bar
kJ/kg
C
Item
Na2S from BLS
Calculation
100*Q17*(78/32)*D11
100*Q17*(78/32)*Q14*L7
Z6+Z7
100*D11*(142/32)*(1-Q17)
10
11
12
13
14
15
16
17
18
Na2CO3
K2CO3
Inert
Total smelt
7
8
9
19
20
21
22
Stoichiometric
Combustion
Products
Oxygen
23
24
25
26
requirement
CO2
H2O
O2 for Na2SO4
O2 for Na2CO3
O2 required for
K2CO3
O2 required for CO2
O2 required for H2O
total O2 required
kg/100 kg BLS
8.78
1.47
10.25
1.78
100*Q14*(142/32)*(1-Q17)*L7
Z9+Z10
100*D12*(58.5/35.5)
100*Q14*(58.5/35.5)*L9
Z12+Z13
100*(106/46)*(D9-(46/32)*D11(23/35.5)*D12)
100*D10*(138.2/78.2)
100*D13 + 100*Q14*L10
Z8+Z11+Z14+Z15+Z16+Z17
(44/12)*(100*D6-(12/106)*Z15(12/138.2)*Z16)
100*D7*(18/2)
Z11*(64/142)
Z15*(48/106)
0.30
2.07
0.99
0.01
1.00
114.46
29.70
0.93
14.15
Z16*(48/138.2)
Z19*(32/44)
Z20*(16/18)
Z21+Z22+Z23+Z24+Z25
0.98
83.24
26.40
125.71
31.25
2.83
0.10
47.50
148
AC
5
6
7
8
9
Air
10
11
12
13
14
15
16
17
18
19
20
AV
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
AE
AF
Water
vapor
in stack
gas
Flue gas
kg/100 kg
BLS
37.04
125.71
88.67
382.19
Item
Oxygen in BLS and saltcake
Total oxygen required
Oxygen required from air
Stoichiometric combustion air
Nitrogen in stoichiometric
combustion air
Forced draft excess air
Total FD air
Infiltration air
Total excess air
Total air flow
Calculation
100*(D8+Q14*L8)
Z26
AF7-AF6
AF8/0.232
AF9*0.768
AF9*Q6
AF9+AF11
AF9*Q7
AF11+AF13
AF9+AF14
293.52
22.93
405.12
34.40
57.33
439.52
100*(1-Q12)/Q12
AF15*Q10
100*Q35
AF16+AF17+AF18
Z19+Z20+AF9+AF14+AF19
42.86
5.71
18.00
66.57
564.01
AW
AX
AY
AZ
4
5
6
7
8
9
AD
Heat
Input
Heat
Output
Item
Heating value of BL solids
Sensible heat in BL
Sensible heat in air
Heat to preheat air
Heat in feedwater for sootblower
steam
Heat in feedwater for blowdown
Total heat input
Sensible heat in dry flue gas
Heat loss from hydrogen in BLS
Heat loss from water in BL
Sensible heat in smelt
Heat of form sulfide
Heat loss from sootblowing steam
Heat loss from blowdown
Radiation loss
Unaccounted losses
Total of losses
Heat to steam
Total heat output
Calculation
D15
(1/Q12)*2.65*(Q13-25)
(AF15/100)*1.006*(Q9-25)
(AF12/100)*1.006*(Q11-Q9)
AF19/100*4.19*(Q36-25)
Q34*4.19*(Q36-25)
AY6+AY7+AY8+AY9+AY10+AY11
(AK7/100)*1.02*(Q21-25)
(Z20/100)*(2770+1.98*(Q21-200))
(1/Q12-1)*(2770+1.98*(Q21-200))
(Z18/100)*Q20
(Z8/100)*12900
(AF19/100)*(2770+1.98*(Q21-200))
Q34*1150
0.3% of heat input
2% of heat input
SUM(AY13:AY21)
AY12-AY22
AY22+AY23
kJ/kg
BLS
13950
314
9
501
%
93.76
2.11
0.06
3.37
64
39
14878
878
829
1196
641
1322
502
127
45
298
5837
9041
14878
0.43
0.26
100
5.90
5.57
8.04
4.31
8.89
3.38
0.85
0.30
2.00
39.23
60.77
100
149
The other independent variables are from the recausticizing and lime burning systems. They are:
Excess lime
Average availability of reburned and make-up lime
Solids in the unwashed lime mud slurry (%)
150
For the sake of practical convenience, there are simplifications and assumptions contained in the
equations. When such simplifications occur, they represent only very small inaccuracies. For
those who are interested in the highest order of accuracy, they can easily revise the equations to
suit their particular needs.
RECAUSTICIZING PLANT MASS BALANCE
Item
Pulp yield
AA on o.d. wood
WL total alkali
WL activity
WL sulfidity on AA
Lime availability
WL spec. grav. 95C
GL spec. grav. 95C
Makeup lime
Item
1. Alkali to Digester
Active Alkali
Total Alkali
2. White Liquor to Digester
White liquor volume
White liquor weight
Weight of chemicals
Water in WL
3. Lime Calculation
NaOH
CaO
Lime
4. Lime Mud Calcination
CaCO3
Inerts
Total Solids
5. White Liquor Clarifier
Underflow Solids
Total Underflow
Liquor
TTA in Underflow as Na2O
Weight of Chemical in Und.
Water in the Clarifier
6. Lime Mud Washer Und.
Uderflow Solids
Recirculation from Filter
Total Solids
Total Underflow
Liquor
TTA in Underflow as Na2O
Unit
%
%
lb/cf
%
%
%
lb/ODT
Amount
48
16.5
7.5
85
25
85
1.13
1.16
22
Calculation
Input Value
Input Value
Input Value
Input Value
Input Value
Input Value
Input Value
Input Value
Input Value
Calculation
lb
lb
687
809
cf
lb
lb
lb
108
7615
1134
6481
809/7.5
108 x 1.13 x 62.4
108 x 10.5
7615 - 1134
lb
lb
lb
516
466
548
687 x 0.75
516 x 56/62
466/.85
lb
lb
lb
832
82
914
466 x 100/56
548-466
832+82
%
lb
lb
lb
lb
lb
40
2285
1371
146
204
1167
Input Value
914/.4
2285-914
(1371/(62.4 x 1.13)) x 7.5
(1371/(62.4 x 1.13)) x 10.5
1371-204
%
%
lb
lb
lb
lb
45
10
1005
2234
1229
21
Input Value
Input Value
914 x 1.1
(914 x 1.1)/.45
2234 - 1005
1229/(62.4 x 1.01) x1.1 Na2O
151
Weight of Chemical in Und.
Water in LMW underflow
7. Green Liquor to Slaker
Total alkali to digester Na2O
Total alkali with lime mud
Alkali in slaker grits as Na2O
Total alkali to slaker as Na2O
lb
lb
31
1198
lb
lb
lb
lb
809
146
1
956
Calculated previously
Calculated previously
Input Value
Calculated previously