EPCP I, Chapter 14
The Kraft Pulping Process1
Conversion of wood chips into a usable paper product requires the separation of many of
the compounds in the chips from the cellulose fibers that constitute the bulk of the wood.
This can be accomplished by dissolution of many of the compounds in the chips in an
alkaline solution. However, such dissolution and subsequent separation of the solution from
the fibers is difficult and requires chemical treatment as well as physical processing. The
kraft process, which will be outlined in this case study, is the result of decades of trial-and-
error experimentation, scientific research, and the application of fundamental engineering
principles.
Before beginning a discussion of the kraft process, we will make several general
observations that may provide an insight into the reasoning behind several of the processing
steps. In the early days of the paper industry, the only requirement for staying in business
was the production of a reasonably acceptable paper, and relatively inefficient but simple
processes were used. There was little incentive for process improvement because the product
was scarce and could be sold at high prices. However, as more and more paper companies
were formed and the supply of paper increased, companies were forced to reduce costs by
making the processes more efficient. Out of this need evolved the process to be described.
As you read the process description, note the steps that have been introduced to
reduce the cost of the final product. Pay particular attention to the recovery and recycle
of unused chemicals, to operations designed to minimize the consumption of utilities such
as steam and water, the combustion of waste chemicals to utilize the energy they contain,
and to processes for the separation and purification of valuable by-products.
PROCESS DESCRIPTION
The major components of wood are cellulose and lignin. Cellulose may be divided into
insoluble (alpha cellulose) and alkali-soluble (hemi-cellulose) fractions. Lignin gives the
wood structural strength, but it must be removed from the cellulose fibers for the formation
of good paper. In its natural state, lignin is a complex, highly insoluble polymer that must
be broken down until its molecular weight and structural characteristics allow dissolution.
Lignin degradation is accomplished by chemical treatment of wood chips. Since many of
the properties of paper depend upon the molecular weight of cellulose in the product, it is
extremely important that the degradation reactions be limited to lignin.
In the kraft process each pound of wood chips is mixed with 3 lb, of solution called
cooking liquor, whose composition is given in Table 14-1. The resulting mixture is then
fed to a digester in which the chips undergo a cooking process that degrades the lignin,
making it alkali-soluble. The cooking process converts the chips to a pulp, which on leaving
the digester is washed with hot water to remove the spent liquor, the lignin decomposition
lReviewed by Ray E. Harrison of Westvaco, Inc.; currently with Weyerhaeuser Co.
products, and fatty and rosin acid salts that were also formed in the digester. The pulp
may then be bleached to increase its brightness or sent directly to a paper-making process.
For the kraft process to be economical, the cooking chemicals must be recovered
from the wash water and spent cooking liquor, which taken together constitute weak black
liquor. This material is subjected to an evaporation step to produce concentrated black
liquor which is then burned; the ash or residue (whatever does not go up the stack) from the
combustion contains the valuable cooking chemicals. The heat produced by burning black
liquor is used to generate steam, which in turn is used to provide heat for the evaporation
operations.
Weak black liquor is converted to a burnable material by concentration in two series
of evaporators. In the first series the solids concentration is increased from 11.6 to 25.0
wt%. (The term solids is used to signify the inorganic materials left over from the cooking
process and the organic materials that result from the degradation of lignin and soluble
cellulose.) Then, to recover valuable nonlignin by-products (rosin and fatty acids), the exit
stream from the initial series of evaporators is fed to a skimming tank where the concentrate
separates into two phases-one rich in crude tall oil (CTO) and the other containing most of
the cooking chemicals. The CTO-rich phase rises to the surface of the liquid in the skimmer
and is drawn off. The aqueous stream containing the cooking chemicals is removed from
the skimmer and sent to a second set of evaporators, where the solids content is increased
to 65.0 wt%.
The concentrated solution from the last evaporator is then fed to a recovery furnace
where the dissolved organic solids burn, evolving heat that is used to generate steam,
and leaving a molten residue of soda ash (sodium carbonate) and sodium sulfide. These
sodium compounds are dissolved in water to to form green liquor, which is treated with
lime (calcium oxide) to convert the soda ash to caustic soda (sodium hydroxide). The lime
is then recovered from calcium carbonate by driving off CO2 in a rotary kiln.
CaO + H20 ---f Ca++ + 20H-
Na2C03 + Ca++ + CaC03 + 2Na’
CaCOa heat CaO + CO2
Crude tall oil from the skimmer contains sodium salts of fatty and rosin acids (soaps),
which are converted to acids by treatment with sulfuric acid, and a nonacidic fraction
called neutrals. The CT0 is then heated and sent through a stripping tower where pitch is
removed as a bottoms product. The overhead stream from the stripping column is then fed
to a distillation column from which purified rosin acids are removed as a bottoms stream,
fatty acid intermediates are removed from the center of the column, and a volatile neutral
fraction is removed as overhead. The fatty acid intermediate is fed to another distillation
column from which distilled tall oil is removed as a bottoms stream, purified fatty acids are
removed from the center of the column, and another volatile neutral fraction is taken off as
overhead.
A schematic diagram of the entire process is shown in Figure 14-1. Three sections of
the process are of major interest: (1) pulp cooking and washing, (2) black liquor evaporation,
acidulation of tall oil soap, and recovery of cooking chemicals, and (3) distillation of crude
tall oil. Detailed drawings of each of these operations are given in Figures 14-2, 14-3, and
14-4. Legends giving information about process streams and conditions are given in Tables
14-1, 142, and 143.
Suppose that you work for a paper company that has been operating a mill for
several years without a good engineering analysis of the process. You have been assigned
the task of completing mass and energy balances on each unit of the process before an overall
assessment of possible modifications is undertaken. The mill produces 1400 tons/day of dry
pulp; the composition of this product stream is given in Table 14-1. You may assume
constant the flow rate of washed pulp (excluding solids, CTO, and water) and the ratio of
water to pulp in streams F, K, and P.
Four evaporator trains have been operating at the conditions shown in Table 142,
and the tall oil refinery at the conditions shown in Table 14-3. Since the composition of
crude tall oil varies with the source of the wood, the compositions shown are approximate. It
has been observed, however, that approximately 30% of the neutrals that enter the process
are nonvolatile and comprise the heavy neutrals portion of pitch. The process is to be
operated so that no more than 1.0% of the entering fatty acids leave in S, and no more
than 5.0% of the entering rosin acids leave in P3.
PROBLEMS
14.1 What is the feed rate of logs (logs/minute) to the process? The logs average 7 ft in
length and 8 in. in diameter.
14.2 If sodium hydroxide costs $0.05 per lb, (1978 estimates), what is the cost of the
sodium hydroxide ($/h) 1 OS t in the washed pulp? Assume all nonfibrous solids in the
washed pulp are NaOH.
14.3 How much crude tall oil (tons/day) is lost in the washed pulp?
14.4 How much fresh water (gal/min) must be fed to the washing operation?
14.5 What fraction of the filtrate from the third filter is slurried with the pulp from the
second filter?
14.6 Determine the weight fractions of crude tall oil and solids in the streams F, K, and
P. For each washer, calculate the ratio of the mass of solids removed from the pulp
stream to the mass of solids fed to the washer. Estimate this ratio for a fourth washer
stae, using a simple extrapolation of the results from the above calculations.
14.7 Calculate the flow rates of all streams in the washer section of the plant. Express
these values in tons/day.
14.8 How much water must be removed from the weak black liquor to produce concentrated
black liquor? Assume perfect separation of crude tall oil and aqueous phases in the
skimmer. Using the compositions given in Table 14-2 calculate the vapor flow rates
leaving evaporators 1 through 5. If it is desirable to limit the vapor velocity to 15
ft/s, what size pipe would you recommend to carry the vapor from each evaporator?
14.9 Assuming that all of the rosin and fatty acids fed to the acidification reactor are
saponified, determine how much sulfuric acid in tons/day must be fed to the reactor
if it is fed in 20% excess. The unsaponified crude tall oil may be assumed to have an
average molecular weight of 335 and one carboxylic acid group per molecule.
14.10 If all of the sodium sulfide from the cooking liquor is recovered, how much water must
be fed to the dissolution tank to produce a green liquor that is 5 wt% sodium sulfide?
What is the sodium carbonate composition in the green liquor?
14.11 At what rate are each of the products from the tall oil refinery produced? Determine
the feed rates to each of the distillation columns.
14.12 The digester operates at 350°F. Assuming the effect of dissolved solids on vapor
pressure to be negligible, at what pressure must the digester operate?
14.13 Ignoring the effect of dissolved solids on the vapor pressure of water, estimate the
pressure in each of evaporators 1 through 5.
14.14 How much 450-psia saturated steam in lb,/h must be condensed isothermally to heat
the cooking liquor-wood chip slurry from 80°F to the cook temperature?
14.15 The blow tank performs several functions, of which one of the most important is heat
recovery. The charge from the digester at 350°F and elevated pressure (see Problem
14.12) is flashed into the blow tank, which operates at atmospheric pressure. The
resultant steam is then used for heating purposes. How much heat (Btu/ton of pulp)
is recovered by the condensation of this steam?
14.16 Estimate the rate at which 450-psia steam must be supplied to evaporator 5.
14.17 Determine the fraction of the heat transferred in evaporator 2 that goes towards the
sensible heating of the liquor fed to this evaporator.
14.18 Solids from the settler carry an equal amount of water (by mass) to the rotary kiln
dryer. Solids plus water enter the dryer at 80°F and the solids leave at 450’F. The
dryer operates at 1 atm. Calculate the amount of heat that must be supplied to the
dryer. Do not forget that the calcining reaction
CaC03 + CaO + CO2
is occurring in the dryer.
14.19 Determine the standard heat of the following reaction, which occurs in solution:
Na2C03 + Ca(OH)2 + 2NaOH + CaC03
14.20 The reactor in which the reaction of Problem 14.19 is conducted operates at 200°F.
Ten percent excess lime is fed to the reactor and the desired reaction goes to 98%
completion. What must be the temperature of the green liquor fed to the reactor?
14.21 You want to do an energy balance on the crude tall oil refinery. Itemize the informa-
tion you need to do this balance as if you were going to ask the operations personnel
of the plant to provide you with the data. Next, suppose they have given you all the
flow rate and composition data you requested, but they are unable to provide any
physical property data. What should you ask your laboratories to measure that will
allow you to complete your task?
Additional Problems for Study
14.22 Suggest additional processing steps necessary for recovery of turpentine from the
vapor leaving the blow tank.
14.23 The last evaporator in the second evaporator train utilizes direct-contact heat trans-
fer; that is, steam is injected directly into the concentrated liquor. Given that clean
steam condensate usually is returned to the boilers where the steam is generated, why
is the direct-contact step used in the last evaporator?
14.24 A possible method of reducing steam costs is to use the hot gases leaving the rotary
kiln dryer in place of steam in the last evaporator. What quantity of these gases
would be required assuming their temperature on exiting the dryer is 250°C and that
they have the properties of air?
14.25 Why is makeup cooking liquor needed? How might the amount of this stream be
reduced?
14.26 Suppose you could separate organic solids from the cooking chemicals in concentrated
black liquor. What would be a major disadvantage to this alternative to combustion
in the recovery furnace?
14.27 Identify potential sources of environmental pollution in the kraft process
TABLE 14-1. Process Information for Pulping and Pulp Washing
P-Washed pulp stream
(a) 15.1% dry pulp - 1400 tons/day
(i) 85% cellulose (alpha cellulose)
(ii) 15% lignin
(b) 0.0939% crude tall oil
(c) 0.136% nonfibrous solids
W-Wood chips
(a) 44.95% Hz0
(b) 53.3% wood
(i) 47% insoluble cellulose (alpha cellulose)
(ii) 23% soluble cellulose (hemicellulose)
(iii) 30% lignin
(c) 1.75% CT0
A-Cooking liquor (SG=l.l)
(a) 3.75 Ib, solids/ft3 solution
(b) 0.2 lb, Ka2S/lb,, solids
(c) 0.6 lb, NaOEI/lb, solids
(d) Other solids may be considered inert
N-Feed to filter 3
1.189% pulp; 0.0368% CTO; 0.2964% solids
Q-Filtrate from filter 3
0.0279% CTO; 0.271% solids
I-Filtrate from filter 2’
0.1581% CTO; 1.391% solids
-H-Feed to Filter 2
1.056% pulp; 0.1722% CTO; 1.4672% solids
C-Filtrate from filter 1
0.4531% CTO; 11.567% solids
D-Feed to filter 1
1.402% pulp; 0.490% CTO; 12.316% solids
TABLE 14-2. Process Information for
Evaporator-Acidification Units
Stream Percent Solids Temperature(OF)
=F 11.6
Ll 21.0 165
J52 25.0 200
L4 30.0 225
L5 38.0 250
L6 55.0 285
L7 65.0
TABLE 14-3. Process Information for the Tall Oil Recovery Units
F,-CT0 feed to column 1
52% fatty acids
42% rosin acids
6% neutrals
PI-Product from column 1 (pitch)
70% heavy neutrals
15% rosin acids
15% fatty acids
P2--Bottom product from column 2 (rosin)
98% rosin acids
2% fatty acids
Sl---Overhead volatiles from column 1
70% neutrals
30% fatty acids
Ps-Sidestream product from column 3 (fatty acid)
90% fatty acids
7% rosin acids
3% neutrals
P4--Bottom product from column 3 (distilled tall oil)
25% rosin acids
75% fatty acids
S2---Overhead from column 3
60% neutrals
40% fatty acids
I I I Steam I I I
I I~~1 Pitch
F I G U R Eb-1. IC - -.
I he Kraft pulping process.
Wash ware,
E J
Washed
DUID
C I f?
L ,
t v
1 ^I _I
stcrage 1 storage 2 storage 3
FIGURE 14-2. Brown stock pulp washers.
To vacuum Evaporators Evaporators Steam vapor
Condensate (to sewer)
CT0
Acidification
Aqueous waste
fcXlOf
FIGURE 14-3. Black liquor concentration and CT0 skimming.
LF2
I
Column 1 Column 2
t
Pi
Pmt. ROSIP
FIGURE 14-4. Tall oil distillation.
