IL
Viiej.:0P1 FOREST PRODUCTS LABORATORY
LI BRARY
LING LIQUOR SYSTEMS
MR COLD SODA PULPINti
No. 2059
December 1956
.FOREST PRODUCTS LABORATORY
MADISON 5, WISCONSIN UNITED STATES DEPARTMENT OF AGRICULTURE
FOREST SERVICE
In Cooperation with the University of Wisconsin
Ni;2.01 FOREST PRODUCTS MORMON,
LIBRARY
1
RECYCLING LIQUOR SYSTEMS FOR COLD SODA PULPINGBy
P. K. BAIRD, Chemist
GIORGIO CERAGIOLI, Research Associate
and
K. J. BROWN, Chemical Engineer
2
Forest Products Laboratory, Forest Service
U. S. Department of Agriculture
Summary
Comparative data on two countercurrent systems for the reuse and recycling of pulping liquors and wash waters in the cold soda pulping
of aspen (Populus tremuloides) were determined. An accelerated batch
pulping process was used in both systems that consisted of impregnating
pre-evacuated chips with solutions of sodium hydroxide at room temperature for 10 minutes under a hydrostatic pressure of 11 atmospheres.
The treated chips were fiberized in a disk mill, and the pulps were
washed in a counterflow system.
In one system, 13 percent of the volume of the fiberizing liquor from
the previous cycle was used, together with each previous drain liquor,
in making up the cooking liquor for the next cycle. Because the
liquors in this partial-reuse system were recycled until the total solids
content of the liquor drained from the treated chips reached 21 percent,
the brightness of the washed pulp decreased from 44.4 percent to
40.6 percent, the bursting strength and breaking length of the pulp
decreased about 10 and 15 percent, respectively, while the pulp yield
increased from 85 percent to 89 percent. Recycling had no effect on
the total amount of caustic soda consumed by reaction, which
averaged about 9 percent, based on the moisture-free weight of the
F
1 or presentation at the TAPPI Alkaline Pulping Conference, New Orleans,
La., November 14-16, 1956.
Maintained at Madison, Wis., in cooperation with the University of
Wisconsin.
Rept. No. 2059 -1-
Agriculture Madison
original wood. The amount of caustic soda in the portion of the
fiberizing liquor that was not reused in this system averaged about 6
percent of the weight of the wood. There was no free sodium hydroxide
in the washed pulps. These results were obtained after making the
equivalent of 60 cooking cycles. In this system, water was used at
the rate of 9,100 gallons of water per ton of moisture-free pulp.
The other liquor reuse system was completely closed. Reusing the
liquors 15 times in this system increased the total solids content of
the liquor drained from the treated chips from an original 1.95 percent
to a final 12.8 percent. The pulp yield increased from 88 percent to
90 percent, and the brightness of the washed pulp decreased from 46
percent to 40.6 percent. There was no change in either the strength
properties of the pulps or in the chemical consumption, which averaged
about 9 percent, based on the weight of the wood. Calculations showed
that if the liquors in this system were renewed after every 15 cycles,
the total chemical requirement would be increased to about 10 percent.
The pH of the washed pulp in the closed system increased from 9.4 to
11.5 during the 15 experiments. The water consumption was 5,560 gallons
per ton of pulp.
The pulps produced in these tests had properties that make them suitable
for use in corrugating board. Higher yield cold soda pulps to be used
as groundwood substitutes in printing papers are made with lower concentrations of caustic soda– It would be expected in this case that the
chemical consumption and the rate of buildup of solubilized organic
matter in the liquors would be somewhat less than for the conditions
used in this study.
Introduction
The cold soda process produces high-yield pulp suitable for corrugating
medium from many hardwood species. With variations of the treatment, it
is possible to obtain pulp that can be substituted for softwood groundwood pulp. Details on the adaptability of the cold soda process to
species, the effects of the pulping conditions on pulp properties, and
other data pn process variations have been reported by Brown and
Carefully controlled caustic soda liquor-penetration
McGovern.
-Brown, K. J., and McGovern, J. N. Production of High-Yield Pulps from
Aspen by Mild Treatment with Sodium Hydroxide. Tappi 33:364-368,
August 1950.
4
Brown, K. J., and McGovern, J. N. High-Yield Cold Soda Pulps and
Products from Several Woods, Paper Industry, April 1953.
Rept. No. 2059
-2-
FO nlEST PRODUCTS LABORATOT
Lt EIHARY
studies were made by Browns by impregnating chips and blocks in a pressure
vessel with solutions of varying concentrations. Several levels and
durations of pressure for impregnation, use of pre-evacuation, and use of
several periods of retention of chemical in the chips before milling were
studied.
The cooking procedure may be carried out by soaking chips for about
2 hours in cold caustic soda solutions followed by disk milling refining.
The treating time can be shortened-by applying hydrostatic pressure.
More recent findings have shown the method to be adaptable to a fast,
continuous procedure in which caustic-wetted chips are subjected to repeated application and release of pressure in a roller mill.
One of the problems in connection with the application of any method has
been the recovery of caustic soda from the spent liquor. An excess of
caustic soda is desirable in treating the chips, and the drain liquor
from the cook or treatment can be fortified and reused. The type of
liquor system employed is also important because it controls the use and
disposal of,chemicals and liquors used in cooking and washing the pulp.
Among the possible applicable liquor systems, the two selected had
countercurrent flow of chips and liquors. One reused as much of the
second-step fiberizing liquor for subsequent cooking liquor volume makeup
as possible, with the balance going to an available alkali recovery
plant. This means that the two wash waters and fiberizing liquors move
countercurrently stepwise in their entirety up to the cooking stage. The
whole system is kept in volume balance by bleeding off the fiberizing
liquor not required for volume makeup of the next cooking liquor. Fresh
water is added at the second washing stage. This is termed the "partialreuse system."
The other, although it has countercurrent movement of chips or pulp and
liquors, transfers only enough liquid from step to step to meet volume
requirements for the next cook. Enough fresh water is added at the
washing or dilution step to replace water lost in the out-flowing pulp
in. excess of the amount coming into the system with the chips. This
is called the "closed liquor system."
The partial-reuse system has definite possibilities where there is a
suitable chemical recovery plant already available to process the excess of partially spent fiberizing liquor. The closed system is of
special interest in the hope of operating successfully without a recovery plant.
5
-Brown,
K. J. Aspects of Cold Soda Pulping in Relation to Penetration.
Report No. 9, Committee on. Coordination of Research, June 2, 1953.
Rept. No. 2059
-3-
It was, therefore, the purpose of these investigations to determine the
limitations of these two selected liquor systems for recovery purposes
and to gather information on chemical consumptions and losses and other
related data.
Experimental Methods
Theoretical consideration of the operation of caustic liquor systems of
the partial-reuse and closed types shows that, at same point, which is
different for each system and set of conditions chosen, the pulp would
become unsatisfactory in quality. The number of satisfactory repetitive
cooks that can actually be made with the same refortified liquors can
be determined only by experimentation with each particular liquor system.
To establish the process conditions that would most probably meet the
Practical commercial limitations of operation, it was considered advantageous to select them from a preliminary study. Then ) with these
conditions chosen, the principal studies would consist of a series'of
similar cooks for each recycling system. The cooks would vary only in
the reaction products present in the reused cooking liquors and in the
effects of such changes in composition on chemical concentrations of the
recycled drain and fiberizing liquors and wash waters, and on the yield,
color, and strength properties and alkalinity of the pulp produced.
Preliminary Study on Effects of Process Conditions
In some of the earlier experiments on the cold soda process, the chips
were treated by steeping. It was decided, however, that better control
of the pulping variables would be Obtained in this preliminary study
by the use of pressure treatment. Also in. this study, the fiberizing
operation. was performed with the digester drain liquor, rather than. with
fresh water as had been done earlier when there was no thought of recovering caustic. The use of drain. liquor in. the attrition mill prolonged the period of chemical reaction, so that less of the total treatment occurred in the digester.
In. the preliminary study,• the cold soda pulping was done in. an 0.5cubic-foot-capacity jacketed digester capable of holding 4 pounds of
-.This study was made by R. Singh, Collaborator, as a course requirement
for the Departnent'of Chemical Engineering, University of Wisconsin,
and was done in 1_954 at the Forest Products Laboratory. The complete results are recorded in an unpublished report.
Rept. No. 2059
-4-
wood chips. The jacket was used as a liquor reservoir for pneumatic
pressure impregnation. Aspen (Populus tremuloides) chips of standard
5/8-inch size and at about 13 percent moisture content were prepared.
The three temperatures chosen. were about 5°, 25°, and 35° C. to simulate
varying mill conditions and give a practical range of experimentation
for the temperature variable. The three concentrations of sodium hydroxide in the cooking liquor were 25, 50, and 75 grams per liter. The
total liquor volume was 5.0 gallons.
The cooks were of 10-minute duration at 11 atmospheres of pneumatic
pressure. This treatment was preceded by an evacuation. to about 26 millimeters of mercury for a few minutes. At the end of the cook, the unabsorbed cooking liquor, termed drain. liquor, was blown, from the digester
and its jacket. The chips were then. dumped from the digester into a
screen box for further liquor drainage and were fiberized in. the 8-inch
Laboratory attrition mill. The combined drain liquors were thoroughly
mixed, measured for volume, and sampled for analysis. The drain liquor
was retained for use in the attrition mill treatment.
A standard setting of the attrition mill plates was selected to give
the desired degree of processing to the pulp for all cooks. The.drain
liquor was recirculated continuously through the mill by a pump from a
sump in the tray collecting the milled chips to furnish a medium to
carry the chips into and pulp out of the mill, and to dissolve and
collect any residual unreacted caustic and solubilized organic matter
held within the chips. This liquor was also used instead of water to
restrict the volume of liquors containing free useable caustic.
The fiberized pulp slurry was then pressed in a hydraulic press to a
dryness of about 35 percent. The combined residual fiberizing liquor
collected at the tray sump and that expressed from the pulp was measured
and sampled.
The pulp cake was broken up / diluted with water to a volume of 7 gallons
(including the residual fiberizing liquor of about 1.2 gallons in the
cake), let set for 10 minutes, and pressed as before. A volume measurement was made on the expressed wash water, and a sample was taken. The
washing operation was then, repeated once more.
The drain liquor, fiberizing liquor, and two wash-water samples were
analyzed for free caustic soda. The residual washed pulp cake was
shredded, mixed, weighed, and sampled for a moisture content determination.
The yield was calculated from these data.
The analyses for free alkali in the raw and cooking liquors, in the
drain and fiberizing liquors, and in the wash waters were made by the
usual volumetric methods.
Rept. No. 2059
-5-
Five of the 9 possible combinations of the 2 major variables (3 temperatures and 3 concentrations) were selected for study. These cooks were
made in duplicate in some instances. The pulping data are given in
table 1. The strength and other test-sheet properties of representative
pulps of this study were determined by standard TAPPI methods. The pulp
testing data are given, in table 2.
temperature.--At a concentration of about 5 1i grams of caustic
per liter, there was only a slight increase in chemical consumption, between 26° C. and 34° C. under the conditions of these experiments. Unfortunately, the data for the consumption at 8° C. were not obtained,
so a wider range of temperature effects could not be evaluated. The
combined consumption of chemical in the digester and in. the mill showed
no regular trend, but these data were not exact because of an intermittent plugging of the attrition mill with consequent temperature rises
of as much as 30° C. in some instances. The plugging was caused by an
inadequate volume of liquid to carry the pulp out of the mill.
Effects of
The effects of temperature an pulp properties were more evident. Data
are given in table 2 for the temperature range from 8° C. to 34° C.
At approximately the same total chemical consumption of 13 percent and
strength properties of the pulps,
at about the same yield of pulp, except tearing resistance, showed increases with temperature increases.
The tearing strength remained constant.
Effects of chemical concentration.--The chemical concentration was
varied from 25 to 76 grams of caustic soda per liter at about 26° C.
As shown, in table 2, an. increase in concentration increased the caustic
consumed from 7.6 to 16.3 percent, on. the moisture-free wood basis.
The pulp yield was reduced from 86 to 78 percent, while the amount of
residual caustic in the pulp increased. In. the standardized recycling
and washing system described earlier, the amount of residual caustic,
although small, increased as the chemical concentration, in. the digester
was increased. All strength properties of the pulps were markedly
lower for each increase in chemical concentration, and suffered an
overall average loss of about 50 percent.
Significance of Results
It can, be observed from this preliminary study that (1) the volumes of
liquors in each step, number of cycles, and concentrations for the particular recycling and washing system chosen should be adjusted to
achieve a minimum final residual caustic content in, the pulp and still
produce a satisfactory product; (2) from a strictly economical standpoint, it is advantageous to operate at the lowest feasible chemical
concentration; (3) the pulp strength values increase (in. the range of
Rept. No. 2059
-6-
86 percent) with increase in yield caused by reducing the chemical
concentration; (4) the amount of fresh wash water required increases
with increasing chemical concentration in the cooking liquors; and
(5) the residual alkali can be washed from the pulp quite easily.
78 to
Partial Reuse of Fiberizing Liquor
with Countercurrent Liquor Flow
0
The flow diagram for a partial-reuse and recycling system for liquors
and wash waters designed to operate in a mill with a recovery plant for
alkaline spent liquors is shown in figure 1. The amount of liquor from
the fiberizing operation that would not be needed for volume makeup of
cooking liquor for the next cook would be diverted to a recovery plant.
Four pounds of aspen chips (moisture-free basis) and 4.0 gallons of
caustic soda solution at 55 grams per liter were used. The moisture
content of the chips was 45.5 percent : which added an additional 0.3
gallon, and brought the chemical concentration down to the desired 50
grams per liter. The digester was evacuated to a pressure of 26 millimeters of mercury before the pneumatic impregnation of the chips at
11 atmospheres for 10 minutes, The temperature was held at 25° ± 1° C.
At the end of this treatment, the excess cooking liquor was blown from
the digester and its jacket, and the chips were dumped from the digester
into a screen box for drainage of any surface liquor.
The drain liquor, which averaged 3.1 gallons, was sampled and combined
with 0.9 gallon of used fiberizing liquor for volume makeup. The
caustic content of the combined liquors was raised to the desired 55
grams per liter by the addition of caustic soda flakes. This solution
was used as the cooking liquor for the next cook.
After the chips drained for a few minutes, they were passed through an
8-inch attrition mill under conditions previously selected to give a
freeness of about 700 milliliters, Canadian Standard. The volume of
liquor added to carry the chips through the mill was 5.8 gallons, which,
together with 1.2 gallons of residual cooking liquor in the chips, made
a total of 7.0 gallons in the fiberizing unit, thus making the fiberizing
consistence 6.5 percent.
The first wash water from the previous cook was used as the fiberizing
liquor. It was obtained by pressing the pulp from the attritionmilled chips in a hydraulic press to about 30 percent dryness on a
moisture-free basis. This first wash water was the "second wash" water
of the previous cook. The pulp from the mill was discharged into a
screened drainer and tray, from which the liquor was recirculated to
the mill by a centrifugal pump. At the end of the fiberizing operation,
Rept. No. 2059 -7-
the pulp was pressed to a dryness of about 30 percent. The expressed
liquor was combined with the recirculated liquor to yield a volume of
about 5.7 gallons of fiberizing liquor, which was analyzed for residual
caustic, total solids, and specific gravity. As previously explained,
about 0.9 gallon was used as liquid makeup for the next cooking liquor.
The balance, or about 4.9 gallons, was withdrawn from the system and
would be sent to the recovery plant in commercial operation.
The pulp cake from the pressing operation was broken up in a 15-gallon
capacity can. for the "first washing" operation. The liquid added came
from the second washing operation of the previous cook. After a
thorough mixing with a mechanical stirrer for 3 minutes, the pulp slurry
was allowed to set for 5 minutes for further extraction of any caustic
from the fibers. The pulp was then dewatered to 30 percent dryness in
a hydraulic press. The expressed liquor from this operation was termed
"first wash water," and was reserved for use as fiberizing liquor for
the next cook. It was also analyzed for amount of caustic soda and
total solids.
The pulp cake was again broken up in a can. for its second and final
wash to remove caustic soda. Fresh water (7.4 gallons) was'added to
give a consistency of 4.7 percent. After it was stirred, as in the previous washing, the pulp was pressed to remove wash water for reuse in
the next cook as first wash water. The balance of the liquor was used
to hold the pulp slurry at about 4 percent consistency for subsequent
operations such as bleaching or refining in the attrition mill. In
this study, the pulp was then. pressed to about 30 percent dryness for
yield determination and subsequent strength tests.
Results of Partial Reuse
of Fiberizing Liquor
In table 3 may be found the values for the caustic content total solids,
alkalinity, and specific gravity of the various liquors used in this
study. In. addition,, the yield and brightness of the pulps were recorded. The data were used to develop the quantitative relations for
the distributional changes of chemicals from cook to cook as shown in
tables 4 and 5.
In. series I of the study, which consisted of 12 identical cooks, the
buildup of solubilized organic matter in the cooking liquor was slow,
as indicated in columns D and E of table 4. To accelerate the rate of
buildup, eight additional cooks (series II) were made in which all the
fiberizing liquor of each was concentrated by evaporation to the proper
volume and used for the makeup. Concentrated liquor from another source
was also added to cycle 19.
Rept. No. 2059
-8-
The values for the properties of the pulp from the last cook in. series II
were used to establish the tolerable limit of contaminating organic matter
for an acceptable product. As shown in table 3, the total solids in. the
drain liquor had built up to over,2O percent. The high viscosity of the
cooking liquor made from the drain liquor apparently lowered the diffusion
rate of the caustic into the chips, with a consequent reduction in. proper
penetration. Examination of the chips showed large, raw centers. This
so reduced the pulping action that the yield increased to 89 percent
(table 5, column P), and the brightness dropped from 44.4 percent to
40.6 percent (G.E.), as shown in. table 3.
The chips contain free caustic and the caustic-combined organic matter
(table 4, columns I : J, K, and L). No doubt a part of the solids is
sodium carbonate, but some of the principal constituents probably are
sodium acetate, sodium uronate, pentosans: and other hemicellulosic
materials, and possibly a. small amount of lignin and sodium lignate.
Under one hypothesis, the caustic penetrating the chips could be taken.
as only that present in the part of the cooking liquor that penetrated
the chips. This value can. be calculated from the volume difference
between the drain. liquor and the cooking liquor. The value (column J,
table 4) for the caustic actually penetrating the chips, which was obtained by difference between. the caustic content of the cooking liquor
and that of the drainaiquor, was found to be greater than the hypotable 4) based on loss of cooking-liquor
thetical value (column
volume.
Since the point of removal of liquor for reuse was at the discharge from
the attrition, mill : a tabulation of the approximate amounts of all
materials entering and leaving the mill was made. These values are
Shawn in tables 4 and 5, and are summarized in columns M, N, and 0 of
table 5. The soluble materials entering the attrition. mill are in. and on
the chips and in. the previous first wash water (table 5, column C) used
as the milling liquor. The milling or fiberizing liquor is the first
wash water of the previous cook plus the cooking liquor in the chips.
Thus, the free caustic and residues of solubilized organic matter removed from the two previous pulps in. their second and first wash waters
are added at this point. The methods for calculating or determining
the amounts of solids present in the various liquors and the amounts
reused are indicated by formulas below the column headings in tables
4 and 5. The overall solids balance for the attrition mill is also
roughly indicated in columns M, N, and 0 of table 5.
Organic matter buildup.--In series I, the amount of solubilized organic
matter present in, the drain. and cooking liquors increases gradually
with each cycle. The composition of the fiberizing liquors coming from
the attrition mill is shown in columns A through F in table 5. The
values in. column F, table 5, show a small gradual increase through the
Rept. No. 2 059
-9-
series that is probably due to an increase in the amount of solubilized
organic matter returning in the wash water and that which was carried
along on the surface of the chips. There is a more definite, but not a
great, increase in the total solids in the fiberizing liquor, as shown
in. column B, table 5. The cooking liquors show a gradvial buildup of
solubilized organic matter, as indicated in columns C, D, and E of
table 4.
In all cases, the maximum useable volume for makeup of the next cooking
liquor, or 12.85 percent of the fiberizing liquor, was combined with
the drain. liquor. Returning with this fiberizing liquor would be 12.85
percent of the solubilized organic matter present in all the fiberizing
liquor. The average value for this quantity for the balance of the
series other than for cook No. 3116X was 338 grams, which is obtained
by reducing the average of column F, table 5, by the average value for
column E, table 5. Again, the same quantity is obtained if the average
value for the combined sodium ion, value (88 grams), column K, table 5,
is added to the average wood loss of 250 grams, as calculated from
column. H, table 5. Therefore, 338 grams of solubilized organic matter
produced in each cook seems to be a firm average value, and 12.85 percent of it would be returned each time with the makeup liquor. The
actual amount for each cook is recorded in column B, table 4.
In. visualizing the mechanism of cooking under the conditions of the
two hypotheses were evolved. Under hypothesis
experiments in series an amount of solubilized organic matter up to as much as that present
in 22.5 percent of the cooking liquor that penetrates the chips could
pass on to the fiberizing liquor after the chips are milled. The data
in. columns C, G, and K are based on. the value of 22.5 percent.
there would be no impregnation of solubilized
Under hypothesis
organic matter into the chips, but some would diffuse or kick back from
the reaction into the cooking liquor and be retained in the drain liquor.
The first hypothesis was tested by comparing the directly calculated
data on amounts of solubilized organic matter with the actual data in.
table 4, and by calculations from equations. The derivation of the
direct data are shown in the subhead for each column, C, G, and K in
this instance. Although the data in column D, table 4, are incomplete,
they do not agree, even roughly, with the calculated data for the cooks
in column C I as developed under hypothesis I. Thisiis also true for
the amounts of solubilized organic matter in the drain liquors, as shown
by comparing column G with 'column H, table 4. It may be seen that the
actual values for the solubilized organic matter present in the cooking
liquor and the drain liquor for any particular cook are considerably
greater than those calculated directly under this first hypothesis.
Rept. No. 2059
-10-
A more precise evaluation of hypothesis I on a mathematical basis was
attempted by means of equations that are developed in the Appendix to
this report. The basic relationships of proportions and movements of
the solubilized organic matter are expressed in the various equations.
The accumulative amount of solubilized organic matter present in the
cooking liquor for each cycle, Sn, was found from equation (4):
Sn , am (1-rn)
1-r
These data, ' when calculated under the assumption of a 22.5 percent impregnation of solubilized organic matter from the cooking liquor into
the chips : were considerably lower than those in column C, and only a
fraction of the actual data in column D. The value for the accumulated
solubilized organic matter for the eighth cycle (n = 8) was calculated
to be only 173 grams. Also : if recycling were continued indefinitely:
the maximum amount of solubilized organic matter that it would be possible to accumulate in the cooking liquor / according to equation (5)2
would be 221 grams. Again : assuming a nominal value for b of 0.01:
which represents 1 percent of impregnation, the S 8 value for equation (4),
that is, the amount of solubilized organic matter accumulatedin the
cooking liquor for the ninth cycle, was found to be 333 grams. This is
still considerably less than the actual data value of 518 grams given
in column. D. These calculated results, then, constitute a second basis
for rejection of hypothesis I. It can be concluded : therefore: that
the assumed conditions in this hypothesis did not represent the actual
cooking mechanism and movement of chemicals.
an equation representing the
To test the validity of hypothesis quantitative relations set forth in this hypothesis was also developed.
The mathematical expressions are given in the Appendix. Under this
hypothesis, it is assumed that there is no impregnation of solubilized
organic matter into the chips, but that there is diffusion of this
matter out of the chips into the cooking liquor.
The value for S at each cycle was obtained by using equation (9) : and
is shown in column E : table 4. The particular value of 0.046 for d„
which was obtained from equation (12) : was used. It represented 4.6
percent of diffusion. It was used so that the value for S 10 in
equation (9) would exactly equal the actual value for solubilized
organic matter as given in column D for cook No. 3132X, or cycle 10.
The data for this cook were deemed the most accurate at that point in
the series. The deviation of the values in column E from column D,
where data is available for comparison : is not large, and the
table
trends are similar.
4,
the viscosity of the cooking liquor had inAt the end of series
creased to the point where a noticeable amount of coating of the chips
Rept. No. 2059
-11-
occurred. This condition would carry some of the solubilized organic
matter present in the cooking liquor along on the chips to the attrition
mill and fiberizing liquor. Only 12.85 percent of this transported
matter would be returned to the drain liquor, while the balance would be
discarded. Consequently, it could be expected that the conditions of
hypothesis I might exist to a small degree simultaneously with those of
hypothesis II, and the residual solubilized organic matter in the drain
liquor and cooking liquor would not build up quite so rapidly. Also,
diffusion out of the chips could stop, which would carry additional
organic matter into the fiberizing liquor. These conditions could
account for the larger differences between values in columns D and E
toward the end of the series. From the close agreement of the values
calculated from the mathematical expression of conditions under hypotheses II with the actual data, it is evident that this hypothesis is
reasonably representative of the mechanisms involved in this pulping
process.
In series II (cycles 13 to 18), where all the solubilized organic matter
was returned in the concentrated fiberizing liquor, the amount of such
matter increased from 641 grams to 930 grams (table, 4, column B). An
additional amount Of solubilized organic matter from a previous series
was added to the concentrated fiberizing liquor from cycle 18. This
produced a large increase in solubilized organic matter in the drain
and fiberizing liquors from cycle 19 used in the cooking liquor of
cycle 20.
At these high concentrations of solubilized organic matter in the cooking
liquors, the highly viscous liquor left a heavy coating on the surface
of the cooked chips. This coating was carried along to the fiberizing
operation, and probably explains some of the loss of solubilized
organic matter from the cooking liquor, as indicated by comparison with
the drain-liquor analysis (table 4, columns D and H). Also, it is
probable that the diffusion of solubilized organic matter from the chips
into the cooking liquor had ceased at this point.
As a result of these high concentrations of solubilized organic matter,
the penetration of the chips became incomplete and the brightness and
velity of the pulp from cook No. 3159X was unsatisfactory. About
3,366 grams of solubilized organic matter, as shown in. column D of
table 4, in 4.0 gallons of cooking liquor used to cook 4.0 pounds of
chips was therefore considered the practical limit. This is 222 grams
of solubilized organic matter per liter, or about 19 percent on a liquor weight basis.
Tolerable maximum number of cooks.--A study of the amounts and distribution of the solubilized organic matter in the cooking liquors, as shown.
in columns D and E, table 4, indicates the progressive rate of buildup
to the maximum tolerable limit (cycle 20) for the production of pulp
with acceptable properties for corrugating purposes.
Rept. No. 2059
-12-
The amounts and distribution calculated under hypothesis II were reasonably close to the actual data available for comparison. Under the con,
ditions of the experiments, there was a gain of 57 grams of solubilized
organic matter per cycle in the cooking liquor. With a limit of 3,366
grams of solubilized organic matter, it would be possible to make about
6o cooks before this value was reached. Then, a part of the drain
liquor would need to be discarded and replaced with fresh liquor after
each cook.
where all the
If the liquor system were operated as in series fiberizing liquor from each cook is evaporated to makeup volume and returned to the cooking liquor, the maximum number of cooks would be con,
trolled by the total solubilized organic matter produced in each cook,
which is 338 grams. This value, then, would produce the limit in. about
10 cooks, after which new cooking liquor would be required.
Effects of recycling on pulp properties.--The brightness of the pulps
gradually decreased in the series from 44.4 percent to 4o.6 percent
(G. E. equivalent) as the dissolved solids going along with the chips'
increased. As indicated in table 3 (cook No. 3153), the difference between the total solids and the caustic soda content in the wash water
(W-1) was about 0.3 gram per liter, which would represent the solubilized organic matter at that point in the washing of the pulp. A
second washing removed all the free caustic, but there was still an
alkalinity of about 0.7 gram of sodium carbonate per liter. Apparently,
the exposure of the pulp to the air during the second washing converted
any residual caustic to carbonate. The effect of recycling, that is,
the increase in solubilized organic matter in the liquors, on the
strength and other properties of the pulps is shown in table 6. It was
felt that the bursting, tensile, and tearing strength values would be
most significant when compared at three freeness levels. Also, the
brightness, pentosan and lignin contents, and yields are indications
of the effects of any buildup of solubilized organic matter, and the
degree of its removal from the pulps by washing.
From table 6, it may be seen. that there was no marked effect of increase of solubilized organic matter in the cooking liquor on the
strength properties of the pulps at three commonly used freenesses.
The pulp from the fresh-liquor cook (No. 3116X) was slightly superior
to those of the subsequent cooks with liquors containing from small
to moderate amounts of solubilized organic matter. In the final cook
(No. 3153X), however, where a maximum tolerable amount of organic matter was present in the cooking liquor, the properties were definitely
reduced, although not seriously, at the same freenesses. When the
pulps were compared at similar sheet densities, only the tearing resistance was lower. This effect could be due to a lower sheet density
being obtained from pulps of the same freeness when the fibers contained sane of the pulping residues. There was little change in the
Rept. No. 2059
-13-
lignin content, but the pentosan value increased 3.3 percent. The
pentosan value of 17.6 percent at a yield of 89.2 percent, when calculated
on the basis of original wood, becomes 15.7 percent. Thus, 2.9 percent
of pentosans were removed by cooking.
Consumption and loss of caustic.--The consumption of caustic for each of
the cooks is given in columns P and Q of table 4. These values were
calculated from the data given in columns M, N, and 0 of table 4. There
was little change in the percentage of caustic that reacted with the wood
from the first to the last cycle. The values ranged between 7.4 percent
and 9.8 percent. It would appear that the increase in yield of pulp, as
shown in column P of table 5, was due to reaction residues left or deposited in the pulp rather than to lower reactivity of the caustic on the
wood.
In addition to the average consumption of 8.4 percent of caustic during
cooking for the series where 12.85 percent of the fiberizing liquor was
returned for cooking liquor volume makeup, an average loss of 7.3 percent
of free caustic would occur by discarding the balance of the fiberizing
liquor. Also, after about 6o cooks, 2 percent of the drain liquor would
have to be discarded to continue operation, which would be an additional
loss of 0.6 percent of free caustic. The total caustic requirement,
therefore, would be about 16.3 percent, based on the wood.
Significance of Results
It is evident from the results obtained by partial reuse of fiberizing
liquors that the conditions of experimentation followed in this study,
where a relatively large amount of caustic was applied to the chips,
would be suitable for economical operations only in conjunction with some
kind of a recovery system. The original concept of operation for a small
cold soda plant obviously did not include a recovery plant. Further work
must be done to determine the feasibility of removing the solUbilized
organic matter from the saturated drain liquor. Another purpose would be
to recover valuable components of the wood that could be processed to
yield furfural or other chemicals.
Complete Recycling of All Liquors
With Single-Stage Pulp Washing
Most of the process conditions for this study were the same as those for
the partial-reuse system. The differences become evident when the flow
of liquors in the two systems shown in figures 1 and 2 are compared. In
the partial-reuse system, shown in figure 1, some of the fiberizing
Rept. No. 2059
-14-
liquor is used for volume makeup for the next cooking liquor. This is
also true for the closed system (fig. 2), but here the similarities
cease. The fiberizing liquor in the partial-reuse system was completely
replaced for each cycle by using the first wash water of the previous
cook. For the closed system, the fiberizing liquor is repeatedly reused,
except for a part that • is removed for makeup of the next cooking liquor.
The fiberizing liquor is then restored to volume for the next milling by
the addition of a part of the wash water from the previous cook.
In the partial-reuse system, the first wash water consists entirely of
the second wash water from the previous cook, while in the closed system,
the first wash water is used repeatedly. The portion that is removed
for fiberizing liquor makeup is replaced by fresh water. As in the first
system, the second wash of the second system consists of fresh water,
but, in addition, it serves as dilution water for transport of the pulp
to the next process.
The results of the previous study were used as a guide in choosing the
following cooking conditions: For 11.0 pounds of aspen chips (moisturefree basis), 4.22 gallons of caustic soda solution were used at a concentration of about 31.6 grams per liter. The moisture content of the
chips was 36.6 percent (green basis), which added an additional 0.277
gallon to the system, and brought the chemical concentration down to
the desired 30 grams per liter. Because three different batches of
chips were used, each with a slightly different moisture content, the
volume and concentration of the liquors had to be varied somewhat for
concentration standardization. The digester was evacuated, as it was in
the partial-reuse system, before the chips were impregnated with the
cooking liquor at 11 atmospheres of pressure for 20 minutes. The
balance of the cooking, fiberizing, and washing procedures were similar
to those of the previous study.
The pressed pulp cake was broken up into a 15-gallon-capacity can for
a single washing. The wash water used came from the previous cook
(1.8 gallons) plus about 1 gallon of fresh water to replace an equal
amount of the wash water that had been drawn off for use in the next
fiberizing-liquor makeup.
After a thorough mixing and dewatering to 30 percent dryness in a hydraulic press, the pulp cake was again broken up into a can for its
final dilution, which in effect corresponded to a second wash. Fresh
water (about 9.0 gallons) was added to give a consistency of 4.0 percent.
The pulp was again stirred and then pressed to remove the dilution water.
The expressed water was sampled and tested for alkalinity and pH value.
In a commercial operation, this pressing would be omitted, and the pulp
slurry would normally be pumped to a bleach plant or paper mill after
it was neutralized or treated. In these studies, the pulp cake was
pressed to about 30 percent dryness for yield determination and titration
Rept. No. 2059
-15-
of a sample for residual alkali in the pulp. Calculations were made to
show how much sulfuric acid would be required per ton of pulp to neutralize
the residual caustic.
Results With the
Closed Liquor System
In. this group of experiments, which consisted of 15 cooks that were
identical in all respects except for the increasing amount of organic
matter in the cooking and other liquors, the effects of a closed liquor
system were rather pronounced. The data on the composition of the
liquors are given in table 7. All cooks had practically the same adjusted
starting concentration of about 30 grams of caustic soda per liter. There
was sane variation in the causticity of the drain liquors and first wash
water from cook to cook that was no doubt due to temperature variations
within. the attrition mill that affected the rate of reaction. The specific
gravity and total solids of the three kinds of liquors showed a gradual
increase through the series, indicating the accumulation. of caustic and
dissolved organic solids.
The closed-system liquors became more nearly saturated with solubilized
Organic matter at the twelfth cycle than did the partial-reuse liquors.
Further comparison. is not possible because of the accelerated loading of
the partial-reuse liquors with solubilized organic matter after the
twelfth cycle. Also in the closed-system series, the pulp characteristics
had not deteriorated to any great extent at,the fifteenth cycle. The
pi-milled chips had not been properly penetrated, however, as evidenced
by the raw centers, which indicates the necessity of further reaction in
the attrition mill, with increased power requirements. The final pulp
brightness of the closed systom reported in table 8 showed a disproportionate drop in relation. to the total solids content of the drain
liquors (tables 7 and 3), however, when compared to the final pulps of
the previous study (table 6).
The amounts of caustic consumed from cook to cook did not change in any
regular fashion or to any marked degree. The average value for the
series was 8.5 percent. Two percent of caustic was lost in the drain
and fiberizing liquors and in the wash water discarded from the final
cook that would be included under the closed system of liquor reuse,
bringing the total alkali consumption to 10.5 percent.
The alkalinity of the pulp gradually increased from a pH value of 9.4 to
11.5 for the final cook. The yield of pulp increased very slightly from
88.1 to 90.5 percent. These and other test data on pulp properties are
given in table 8.
Rept. No. 2059
-16-
If the process conditions used in this closed-liquor system study were
followed, about 5,560 gallons of water would be required per ton of pulp
product. This is a very favorable factor in same areas.
Significance of Results
The decision as to the maximum number of cooks that could be made with
one batch of liquor under the closed liquor system was based on the poor
penetration of cooking liquor into the chips and on the high alkalinity
of the pulp from the last cook (cycle 15) of the series, as well as
the build-up of organic matter in the drain liquor and the pulp quality.
The data in table 7 indicate that 38 pounds of sulfuric acid per ton
of pulp would be required for neutralization of the residual free alkali.
Also, the properties of this pulp approached the least acceptable
standards set in the partial-reuse system study.
It would seem, therefore, that only about 15 cooks could be made under
the closed liquor system before the liquors would have to be replaced.
Under these circumstances, the question of periodic replacement of
liquors arises. Such operations are not in accord with usual industrial
practices. Continuous instead of periodic withdrawal of drain liquor to
hold down the amount of solubilized organic matter, however, would remove a disproportionate amount of free caustic, and could make the
operation uneconomical.
These facts, then, indicate the need for some kind of a recovery system
for the periodically discarded liquors. The pentosans might be removed
and marketed, and the free caustic recovered if the plant produces
liquors in sufficient quantity, or the alkali in the liquors could be
utilized by the pretreatment of raw chips. The residual organic matter
might then be removed by ponding, or it could be concentrated and sprayburned for fuel. Obviously, further research is indicated to develop
such ideas.
Conclusions
The conclusions for the two systems for liquor reuse and recirculation
were drawn on the basis of the following specific conditions of experimentation: Chemical concentrations of 30 and 50 grams of caustic
Rept. Uo. 2059
-17-
soda per liter, applied for 20 and 10 minutes, respectively, at about
25° C.; an impregnating pressure of 150 pounds per square inch (gage)
after evacuation to about 25 millimeters of mercury for 5 minutes; a
liquor-to-wood ratio of about 5 to 1 in the digestion zone; and a degree
of digestion to give about a 90 percent final yield of pulp suitable for
corrugating board.
System applicability.--Both methods of reusing and recirculating the
liquors appear to be feasible. One requires the availability of a chemical recovery or disposal unit, while the other possibly does not, but
functions as a closed system requiring a complete renewal of the principal liquors periodically.
Pulp alkalinity.--An alkali-free pulp can be obtained with two stages
of countercurrent washing under the partial-reuse system, where a maximum
of about 13 percent of the fiberizing liquor can be utilized for cookingliquor makeup. In the closed liquor system, the pulp produced has a high
residual alkalinity (pH 11.5) due to free caustic soda.
Chemical consumption and loss.--The average chemical requirement for
cooking under the partial-reuse liquor system is 8.4 percent, on the basis
of moisture-free wood. An additional 7.3 percent is lost in the discarded
portion of the fiberizing liquor if a recovery plant is not available.
Also, after about 6o cooks, 0.6 percent more caustic is lost with the
discarded drain liquor (it would be necessary to remove 2 percent of the
drain liquor after each cook to maintain a solids balance). The total
caustic requirement, therefore, is 16.3 percent.
If a consistency higher than 6.4 percent is used in the fiberizing
operation, the fiberizing liquor can be reused more times, with a consequent reduction in chemical losses. More solubilized organic matter
will be returned to the cooking liquor, however, which in turn will reduce the number of cycles before unsatisfactory pulp would be obtained.
For the closed liquor system, the average chemical consumption is 8.5
percent. To this value must be added a 2 percent loss with the periodic
discarding of the drain and fiberizing liquors and wash waters after about
15 cycles. A total of 10.5 percent of caustic is therefore required for
this type of operation. For groundwood substitute pulp, the pulp need
not be neutralized, and some of the caustic could be charged to the
bleaching operations, which require a high alkalinity.
Reuse cycles.--The number of times that liquors can be reused before a
certain maximum concentration of solubilized organic matter accumulates
in the cooking liquor can be calculated from the mathematical equations
developed for any set of reuse conditions. If all the fiberizing liquor
is reused, either after it is concentrated to required makeup volume or
as in the closed system, then about 15 cooks, based on final corrugating
Rept. No. 2 059
-18-
pulp quality, can be made. If about 13 percent of the fiberizing liquor
is reused for volume makeup, then as many as 60 cooks can be made with a
single batch of liquors before additional discarding of some drain liquor
is necessary.
Water requirements.--A total of about 9,100 gallons of fresh water per
ton of pulp would be required to give an alkali-free pulp with the partial-reuse liquor system. For the closed system with one stage of washing,
a total of about 5,560 gallons would be needed. The pulp produced would
be highly alkaline, however. These values include the final dilution of
the pulp for pumping to the next process.
Process feasibility.--Prom the standpoint of caustic losses alone, the
closed liquor-reuse system is considered to be economically feasible
without a chemical recovery plant, provided a periodic type of liquor
disposal and renewal is practiced. This requires the tolerance of some
variability in pulp properties during each disposal cycle, and an unusual procedure for operating a pulp-mill liquor system. Only about 15
cycles of reuse are possible, however, before the quantity of solubilized organic matter in the cooking liquors inhibits good pulping. The
problem of disposal of the loaded and discarded liquors has not yet been
solved.
The partial-reuse system is not feasible without a recovery plant, especially because of the high chemical losses, and, to a degree, from
the liquor-contamination standpoint.
Theoretical calculations based on data from other work indicate that
continuous pulping systems would have about the same limitations in the
reuse of liquors due to their eventual contamination with solubilized
organic matter. Continuous operation holds the greatest promise, provided the continuous disposal of a part of the liquors can be tolerated.
Rept. No. 2059
-19-
APPENDIX
The derivations of the equations expressing mathematically the relations
stated in the two hypotheses are given in this Appendix.' These equations
were used to evaluate the results and confirm or disprove the mechanisms
controlling the cooking (impregnating) of wood chips with caustic soda
solutions by the cold soda pulping process.
The cold soda process is a two-phase system of liquid and-solid (chips),
with the solid being impregnated with a part of the liquid phase. The
chips are removed from the impregnating operation and reduced mechanically
to fibrous form in another liquid. The liquid is then pressed from the
fibrous solids, and a part of it is retained for subsequent use in the
next cooking liquor. This part carries with it some of, the soluble extracted reaction product, which is then present in the next cooking
liquor. The process is repeated over and over with new chips, reusing
the same liquors refortified with dry caustic until the pulp is no
longer acceptable due to contamination with the reaction residues.
Hypothesis I
Under hypothesis I, it is assumed that: (1) any amount of the reaction
residues, up to all present in the part of the cooking liquor that penetrates the chips, is impregnated into the chips; (2) a certain negligible
amount of the reaction residues diffuses out of the chips into the
cooking liquor; and (3) a part of the fiberizing liquor, containing a
portion of reaction residues, is reused for volume makeup of the next
cooking liquor.
Let m represent the total reaction residue from one cook; a the part
of the residue in the fiberizing liquor returned for reuse; b the part
of the residue in the cooking liquor impregnated into the chips; and 1-b
the part of the residue left in the drain liquor. The following values
for the, quantities are constant: m = 338 grams; a = 0.1285, or 12.85
percent; and b = 0.275, or 27.5 percent.
From the first cook, the amount of residue returned with the fiberizing
liquor makeup for the second cook is am grams. For the second cook,
the amount of reaction residues impregnated is bam, while that retained
in the drain liquor is (1-b)am. The amount returned for the next cook
is a(m+bam) grams. For the third cook, the cooking liquor contains
(1-b)am + a(m+bam), or am(2-b+ab) grams of residue. The amount impregnated is bam(2-b+ab), while that remaining in the drain liquor is
am(1-b) (2-b+ab) grams. The amount returned for the next cook is:
a(m+bam 2-b+ab)).
Rept. No. 2059
-20-
The amount of reaction residues present in the cooking liquor of the
fourth cook is then% am(1-b) (2-b+ab) + a[m+bam (2-b+ab)] or,
am [1 + (2-b+ab) (1-b+db)] grams. From the fourth cycle, the amount returned is expressed by the quantity: am(1 + [1 + (2-b+ab) (1-b+ab)]
(1)
(1-b+ab))
If r is equated to (1-b+db) then the above quantity (1) can be expressed
(2)
as: am(1 + [1 + (l+r) r] r) or, am(1 + r + r 2 + 1-1 ) grams.
For the n th Rycle then, the amount of residues returned is:
+ r) + ----rn-1 ) grams.
am(1 +
This is a geometric series, the equation for the sum of which is:
s n = am (1-rn)
1-r
If the process is carried on indefinitely, then the amount of reaction
residues returned from each cook approaches the value for S with n at
infinity:
co
am
_ 1-r
grams
(5)
To determine the number of cycles, n, required to raise the amount returned to the value for S n , the following equation, derived from
equation (4), is applicable:
Sn
(6)
n log [1 - Fru (1-r)]
log r
For the value of a that will result in a certain value for S when n is
infinite, the following equation applies:
b
a- m+b
grams
(7)
am grams
(8)
Or, for b, given So:
b Rept. No. 2059
1 - a
-21-
Sop
Hypothesis II
Under hypothesis II, it is assumed that: (1) none of the reaction
residue penetrates the chips during cooking; (2) some of the residue
diffuses out of the chips into the cooking liquor around the chips; and
(3) a part of the fiberizing liquor, containing a portion of reaction
residue, is reused in the next cooking liquor.
Let m represent the total reaction residue from each cook; d the part of
residue diffusing back into the cooking liquor that becomes drain liquor;
the balance, or 1-d, the part present in the fiberized chips (pulp); and
a the part of (1:a7m that is returned with some of the fiberizing liquor
TO the drain liquor for volume makeup.
In the first cook, dm grams are removed by diffusion from the chips into
the cooking (drain) liquor, and am(1-d) is returned in the fiberizing
liquor to the drain liquor.
The cooking liquor of the second cook, therefore, contains dm + am(1-d)
grams of residue. Its drain liquor contains dm + [dm + am (1-d)] grams.
The cooking liquor of the third cook contains dm + [dm + am (1-d)] plus
a returned amount of am (1-d) grams. Its drain liquor contains:
dm + dm + [dm + am (1-d)] + am (1-d), or 3dm + 2am (1-d) grams.
The cooking liquor for the fourth cook contains:
3m [d + a - ad] grams,
while that for the fifth cook contains:
41:11
[d + a - ad] grams.
For the n th cook, then, the residue in the cooking liquor is equal to:
Sn = m(n-1) (d+a-ad) grams.
If the quantity (d4a-ad) is equated to
T;-1 i
r,
then:
"inns.
Solving equation (9) for n, r, and d gives:
Sr,
n = MY
- + 1
r = Sn
m (n-1)
Rept. No. 2059
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