BACKGROUND AND SUMMARY OF THE INVENTION
[0001] The present invention relates to a method of producing kraft pulp by cooking comminuted
cellulosic fibrous material with white liquor to produce kraft pulp and black liquor,
whereby
(a) a slurry of cellulosic fibrous material is treated in a plurality of consecutive
stages with white liquor, including at least first and second stages, using a first
supply of white liquor to the first stage and a second supply to the second stage,
the first supply of white liquor having a sulfur content greater than the sulfur content
of the second supply of white liquor;
(b) the material treated with white liquor is subjected to cooking conditions in at
least one of the stages to effect kraft cooking thereof, and black liquor is produced.
[0002] For many years it has been known that a higher sulfide concentration in white liquor
for kraft pulping in the pulp and paper industry (i.e. higher white liquor sulfur
content) could produce kraft pulp with higher viscosity and better physical properties.
It has also been known that the beneficial effect of higher white liquor sulfur content
is more profound in the early stages of the kraft cook than in the later stages (S.
Nordén and A. Teder, Tappi, vol. 62, no. 7, July 1979, p. 49-51; B. Johannson et al,
Svensk Papperstidning no. 10, 1984, p. 30-35). For improving the conditions in the
initial phase S. Nordén and A. Teder describe to use two separate white liquors with
different sulfidities. The higher-sulfidity liquor can be used in the impregnation
and the lower-sulfidity liquor introduced later, e.g. in the transfer circulation
or in the first pulping circuit. It is well-known, as dislosed in J.P. Casey "Pulp
and Paper"; Chemistry and Chemical Technology 3rd ed., vol. I, 1980, John Wiley &
Sons, New York, p. 470-476, that sulfur-containing gases are released during the digester
relief and blow, from condensate stripping, and from other sources.
[0003] Several methods, including absorption in white liquor, has been proposed to treat
said gases. However in the past there have been a number of technical and practical
concerns and conditions which have precluded practical utilization of these concepts.
Similarly maximum utilization has not been commercially made of the known ability
of polysulfide to stabilize carbohydrates and wood against degradation during chemical
pulping by oxidatively converting the reducing end groups in celluloses and hemi-cellulose
to carboxylic groups (US-A-2,944,928).
[0004] According to the present invention, a method of producing kraft pulp from cellulosic
comminuted fibrous material utilizing white liquor, as described above, is provided.
The invention is thereby characterized by the following steps: (c) sulfur from the
black liquor is recovered by heating the black liquor to produce sulfur-containing
off gases; and (d) the recovered sulfur is added to a stream of white liquor made
from the remaining black liquor to increase the sulfur content thereof thereby producing
said first supply of white liquor deriving from said remaining black liquor.
[0005] In a preferred embodiment of the inventive method the off gases are treated to produce
primarily methane and hydrogen sulfide. Preferably the hydrogen sulfide from the treated
off gases is fed to a scrubber in which it is brought into contact with white liquor,
thereby producing said first supply of white liquor so that an optimum viscosity/kappa
ratio can be achieved.
[0006] According to the most specific aspects of the present invention, the concepts described
above are utilized in a practical manner to provide kraft pulp that has an optimum
viscosity/kappa ratio, and/or good strength properties, and with good yield. The invention
is applicable to a wide variety of different kraft cooking processes, both batch and
continuous. For example the invention can be utilized in continuous digesters having
an impregnation zone, or in cooking systems utilizing a separate impregnation vessel
from the continuous digester, or in batch digester. The invention can also be utilized
in association with co-current movements of white liquor with the pulp, or countercurrent
movements, such as are provided in the commercial digesting process marketed by Kamyr,
Inc. of Glens Falls, New York under the trademark "MCC".
[0007] White liqour is that treatment liquid in a kraft process which contains the active
cooking chemicals, sodium hydroxide (NaOH) and sodium sulfide (Na
2S); or white liquor in an extreme situation may contain substantially only NaOH as
active ingredient. According to standard practice, the white liquor sulfur content
in the cook is maintained in the range of 25-35 % (this overall sulfur content ratio
is the amount of sodium sulfide to the sum of sodium sulfide and sodium hydroxide
applied to the whole cooking process), and according to standard practice in the art,
a sulfur content level below 15 % results in a deterioration in the cooking rate and
pulp quality. During the production of kraft pulp, residual or "black liquor" containing
the reaction products of lignin solublization is whithdrawn from the digester, concentrated,
and burned in a recovery furnace to yield an inorganic smelt of sodium carbonate and
sodium sulfide. The smelt is dissolved to form green liquor which is reacted with
quick lime (CaO) to convert the sodium carbonate into sodium hydroxide and thereby
regenerate the original white liquor.
[0008] According to the present invention, it has been found that by making two (or more)
supplies or streams of white liquor, with different sulfur contents, and applying
them to different portions in the kraft cycle, significantly improved results can
be achieved. In fact it has been found that it is highly desirable to add the majority
of the sulfide in the total white liquor (total cooking chemical) -- at least about
60-90 %, in fact even almost all the sulfide -- at the initial stages (e.g. impregnation)
of the kraft cycle, while adding white liquor with primarily only sodium hydroxide
at the later stages (e.g. co-current or countercurrent cooks). Practicing the invention,
it is possible to optimize the viscosity/kappa ratio of the produced pulp for any
given level of sulfur content, and/or to optimize pulp strength properties. The increase
can be dramatic, easily on the order of 25 % for conventional cooks with multiple
white liquor additions (co-current), about the same increase for modified continuous
cooking (MMC™), and 15 % or more for extended modified continuous cooking (EMMC™).
Comparable increases occur for batch treatment too.
[0009] When about 2 % polysulfide on wood, expressed as elemental sulfur, is provided in
the white liquor, a yield equal to kappa 18-20 for a conventional kraft cook is produced
with a kappa of about 12.5, and pulp with a viscosity comparable to conventional cook
kraft pulp at a kappa of about 26 is produced. Elemental sulfur (in dry or slurry
form) may be used instead of polysulfide; elemental sulfur is about 60-75 % as effective
as polysulfide.
[0010] While the exact source of the sulfur for producing the high sulfur content stream
or supply of white liquor according to the invention is not critical as long as the
sulfur is recovered according to step (c) of claim 1, one exceptionally good source
that allows a practical, industrial scale process to be practiced is that shown in
US-A-4,929,307 wherein sulfate black liquor is heated to above the cooking temperature
so as to split the macro-molecular lignin fraction, to produce sulfur-containing off
gases. Those off gases are favourably reacted to produce primarily methane and hydrogen
sulfide, and then brought into contact with sulfur depleted white liquor from the
normal chemical manufacturing facility of the pulp mill, to produce an extremely high
sulfur content white liquor, the hydrogen sulfide being selectively absorbed into
the white liquor. That high sulfur content white liquor may then be acted upon to
produce at least some significant portions of polysulfide, and then utilized in early
stages of the kraft cook.
[0011] The cooking liquor utilized above is a kraft cooking liquor. It may contain anthraquinone
or its derivatives or equivalents, or the like, and the first liquor may be targeted
to an impregnation stage, co-current cook stage, or countercurrent cook stage.
[0012] It is the primary object of the present invention to provide a substantially improved
cook cycle for the production of paper pulp. This and other objects of the invention
will become clear from an inspection of the detailed description of the invention,
and from the appended claims.
BRIEF DESCRIPTION OF THE DRAWING
[0013] FIGURE 1 is a schematic view of exemplary apparatus for practicing an exemplary method
according to the present invention.
DETAILED DESCRIPTION OF THE DRAWING
[0014] FIGURE 1 illustrates exemplary apparatus for use in kraft pulping process.
[0015] In a typical kraft pulping process, as illustrated in FIGURE 1, a digester 12 --
which preferably is a continuous digester such as that sold by Kamyr, Inc. of Glens
Falls, New York, but may be a batch digester -- has a stream of off gases 13, and
black liquor (residual white liquor containing the reaction products of lignin solubilization)
is withdrawn at an intermediate position as indicated at 14, while the kraft pulp
produced is discharged at 15. When the black liquor in line 14 is discharged, it may
be passed directly to black liquor evaporators, and preferably it is subjected, somewhere
in the evaporator chain, to a heat treatment process at step 17 to produce off gases
in line 18. The heat treatment of block 17 is preferably that described in US-A-4,929,307.
After heat treatment at 17 the black liquor passes to evaporators 19 (evaporator 19'
may concentrate the black liquor before heat treatment 17 too), which also produce
off gases in line 20, then to a conventional recovery boiler 22, with conventional
white liquor manufacture at block 23, to produce white liquor in line 24 having depleted
sulfur content.
[0016] The off gases in 18 -- which may include only those from the heat treatment 17, or
also those from the digester line 13, only and from the black liquor evaporators in
line 20, or a combination of any two of them -- are preferably first subjected to
a drying or absorption stage (as indicated schematically at 27 in FIGURE 1) in order
ro remove a majority of the water vapor. The removal of the water vapor increases
the concentration of organic sulfur gases. Step 27 is accomplished by drying the gas
stream by any conventional means and/or by absorbing or adsorbing the organic portion
of the gas onto a solid, or additionally by absorbing the off gas into one of any
non-polar liquids (e.g.kerosene or mineral oil). Treatment may be provided of a liquid
mixture, but preferably according to the invention further treatment is of the concentrated
gas.
[0017] The next steps in the treatment of the off gases as illustrated in FIGURE 1 are to
add hydrogen, and the pass the gas in the presence of the added hydrogen past a hydrogen
desulfurization catalyst. This may be accomplished, for example, in the hydrogen desulfurization
(HDS) unit 28, with the hydrogen gas from line 29 added to the unit 28 along with
the gas in line 18. The hydrogen gas in line 29 can come from any source (e.g. be
purchased, from water electrolysis, etc.). It is preferred that the hydrogen desulfurization
catalyst consist essentially of a transition metal-molybdenum alloy, particularly
a nickel molybdenum or cobalt molybdenum alloy.
[0018] Typically, in gaseous processing, the product gas stream in line 30 is further acted
upon. The gas stream in line 30 contains primarily methane, and hydrogen sulfide,
with hydrogen also present. Preferably the hydrogen sulfide is then separated out
from the gas in stream 30. While the hydrogen sulfide may be separated as a gas and
then used in its gaseous form in conventional pulping techniques, it may be fed to
a scrubber 32 in which it is brought into contact with a caustic solution, preferably
kraft white liquor, which contains sodium hydroxide and most likely at least some
sodium sulfide. While in the preferred embodiment illustrated in the drawings white
liquor is utilized, under some circumstances green liquor may be advantageously utilized,
with white liquor subsequently made from the green liquor.
[0019] White liquor from line 24 is passed into inlet 33 of scrubber 32, the hydrogen sulfide
being absorbed in the white liquor and thereby significantly enhancing its sulfur
content. The significantly enhanced sulfur content white liquor then passes through
the outlet 34 of the scrubber into line 35, to be used in the pulping process. Desirably,
the white liquor in line 35 passes through a polysulfide treatment stage, as illustrated
at 36, and then to the impregnation vessel 37 (if a separate impregnation vessel is
used) or the like, to be utilized in the pulping cycle. Elemental sulfur may be added
at 36 instead of polysulfide.
[0020] The gas stream that remains, in line 38, contains primarily methane, but also some
hydrogen. Ultimately, the gas in line 38 may become the source of the hydrogen for
line 29.
[0021] According to the invention, the high sulfur content white liquor in line 35 is provided
at an early stage of the cook, e.g. at the beginning of the impregnation vessel 37,
or impregnation stage if impregnation takes place in the digester 12 itself, or at
multiple places in the impregnation zone and/or vessel 37. A countercurrent impregnation
flow may be provided, in which case the higher sulfur content liquor is added near
the end of the impregnation stage. Part of the sulfide depleted white liquor in line
24 is passed into line 41, and it is then introduced into the cook, preferably at
multiple locations, as indicated at 42 and 43 in FIGURE 1.
[0022] According to the invention, where the low sulfur content white liquor in line 41
is introduced into the kraft cook may vary widely. For example, it may be added to
the middle of the impregnation vessel 37, at one, two, or more co-current stages in
the digester 12, or at one, two, or more countercurrent stages in the digester 12
(e.g. for modified continuous cooking, or extended modified continuous cooking). Of
course, the liquor in line 41 may also be utilized in a batch process.
[0023] While the drawing illustrates only two streams or supplies of white liquor, 35, 41,
having different sulfur content, as many different sulfur content streams as desired
may be produced. For example two series connected units 32 may be utilized, the first
producing the highest sulfur content level white liquor, while the second produces
an intermediate (between lines 35 and 41) sulfur content level white liquor. The intermediate
sufidity white liquor is added earlier in the cook than the white liquor in line 41.
[0024] The relative amount of sulfur content of the white liquor added at various stages
within the kraft cycle may also be varied widely according to the invention. For example,
if the kraft pulping process is to be a multi-level conventional cook, that is white
liquor is added at two or more points in the cook and flows co-currently with the
pulp, then about 60% of the total cooking chemical is added to the impregnation vessel
(e.g. in line 35), while about 25% is added to the first co-current stage (e.g. at
42) and about 15% to the second co-current stage (e.g. at 43). In this procedure,
preferably the amount of sulfide provided in line 35 is about 60-90%, and if practical
may be almost 100% of the total sulfide in all of the white liquor streams, that is
the white liquor in stream 41 is substantially fully sulfide depleted. The stream
in line 35 in this embodiment may be generated by passing 35-65% of the total volume
of white liquor through the unit 32, the remaining 65-35% of the white liquor being
added through line 41. According to another embodiment, about 35% of the total volume
of white liquor is passed through unit 32, and this high sulfur content white liquor
is then added to the top circulation in the conventional impregnation vessel 37. The
sulfide-depleted white liquor in line 41 is added to middle circulation in the vessel
37 in the amount of about 25-35% of the total cooking chemical from white liquor,
while about 20-25% of the total cooking chemical, in the sulfide depleted white liquor
in line 41, is added to the continuous digester 12 first cooking circulation.
[0025] The low sodium sulfide content liquor in line 41 may also be added at 44 to an oxygen
delignification or bleaching stage 45 as a source of sodium hydroxide.
[0026] When utilizing the multiple level sulphidity white liquors according to the invention
in modified continuous cooking and extended modified continuous cooking sequences,
the viscosity to kappa ratio may be increased by about 0.2-0.3 units if almost all
sulfide is added to the impregnation stage (e.g. in line 35 to vessel 37). Preferably
at least about 60% (e.g. 60-90%) of the total sulfur content is added in the impregnation
stage (line 35), the total volume of white liquor added in line 35 being about 40-65%
of the total volume of white liquor used in the pulping process.
[0027] In stage 36, polysulfide is added to the white liquor. For example, this can be done
by the MOXY (TM) process in which some of the sodium sulfide in the white liquor is
partially oxidized to produce polysulfide, or by other known polysulfide processes.
Alternatively, in stage 36 polysulfide from an external source may merely be introduced
into the white liquor, e.g. polysulfide produced by reacting elemental sulfur with
sulfide ions in an aqueous solution under proper conditions; or elemental sulfur may
be added to the white liquor instead of polysulfide.
[0028] The amount of polysulfide produced, or added, in stage 36 is about 0.5%-8% on wood,
expressed as elemental sulfur. Typically, about 2% polysulfide is desirable. If 2%
polysulfide is used in conjunction with extended modified continuous cooking, a kraft
pulp with a kappa of about 12.5, a viscosity of about 33.7 cp, and a yield of about
44.6% can be made. This yield is equal to that of a conventional cook or extended
modified continuous cook pulp at a kappa of about 18-20 without polysulfide, and the
viscosity is equivalent to that of a conventional cook pulp at kappa 26, or an extended
modified continuous cook pulp at kappa 17.
[0029] If an amount of elemental sulfur equivalent to about 0.5-8% polysulfide is used,
the results are about 60-75% as good as when polysulfide is used.
[0030] Utilizing the apparatus schematically illustrated in the drawings, various methods
may be practiced according to the invention. According to one method:
(a) Two (or more) streams of white liquor, 35, 41, are made up, the first stream (35)
having relatively high sulfur content, and the second (41) relatively low sulfur content
(even approaching zero).
(b) Cellulosic comminuted fibrous material (e.g. wood chips) are impregnated with
the first stream 35 (e.g. in vessel 37).
(c) The material is cooked under kraft cooking conditions, in a cooking zone (in vessel
12) with cooking chemicals (the sodium hydroxide and sodium sulfide in the white liquor)
to produce kraft pulp.
(d) The second stream, 41, of white liquor is supplied to the cooking zone (e.g. digester
12) as cooking chemicals; and
(e) the kraft pulp is washed (e.g. in a wash zone in digester 12, and/or in a separate
wash vessel).
[0031] According to another aspect of the invention, a slurry of wood chips is treated in
a plurality of consecutive stages (e.g. impregnation stage, first and second co-current
or countercurrent cooking stages) with white liquor using first and second supplies,
differing in the sulfur content thereof. The chips are treated with white liquor under
cooking conditions (e.g. in digester 12) in at least one stage, to effect kraft cooking
thereof. Black liquor is withdrawn (at 14) and sulfur is recovered from the black
liquor, as by heating treating it (at 17) according to the process of US-A-4,929,307,
evaporating it (in 19), etc. (see 22 and 23 in FIGURE 1). The recovered sulfur is
added to the first supply of white liquor, as in unit 32, to significantly increase
the sulfur content thereof, so that the sulfur content of the liquor in line 35 is
substantially greater than that in line 24 (which is sulfur depleted, and may be near
zero). The relative sulfur contents of the white liquors in lines 35 and 24 are controlled
so as to optimize the viscosity/kappa ratio and/or physical strength properties.
[0032] The invention allows advantageous production of kraft pulp to be practiced on an
industrial scale -- that is, larger production than reasonably possible in a laboratory,
with complete chemical recovery.
[0033] The invention may be illustrated by various examples.
[0034] Tables IA-IE provide the results of laboratory batch cooks using split white liquor
streams with variable sulfur content, according to the invention, and conventional
cooks for comparison purposes. In these tables, "CK" means conventional kraft cooking,
"MCK" means kraft cooking with multiple introductions of white liquor, with more than
one co-current cooking stage, "MCC" refers to Kamyr, Inc.'s trademarked modified continuous
cooking process in which multiple introductions of white liquor are provided, and
a countercurrent cook stage, and "EMCC" refers to Kamyr, Inc.'s trademarked extended
modified continuous cooking process in which a second countercurrent cook is provided.
[0035] Table II illustrates the advantages achieved when polysulfide is used. The liquid
to wood ratio for all cooks in Table II is 4/1. "Sulfidity" refers to sodium sulfide
content.
[0036] The wood utilized in all of TABLES IA-E and II is southern pine from the Mississippi
area. However, the results are applicable to a wide variety of wood species.
TABLE II
| Cook number |
A2961 |
A2958 |
A2962 |
A2959 |
A2960 |
A2963 |
| Type |
EMCC |
EMCC |
EMCC |
MCK |
MCK |
EMCC |
| Polysulfide, % |
2 |
2 |
3 |
2 |
3 |
nil |
| |
| PRESTEAMING: |
|
|
|
|
|
|
| Time, min |
5 |
5 |
5 |
5 |
5 |
5 |
| Temperature, °C |
110 |
110 |
110 |
110 |
110 |
110 |
| |
| IMPREGNATION: |
|
|
|
|
|
|
| Time, min |
30 |
30 |
30 |
30 |
30 |
30 |
| Temperature, °C |
110 |
110 |
110 |
110 |
110 |
110 |
| Pressure, kPa (psig) |
1034 (150) |
1034 (150) |
1034 (150) |
1034 (150) |
1034 (150) |
1034 (150) |
| Initial EA, % NaOH |
12 |
16 |
13 |
- |
- |
12 |
| Initial EA, % Na2O |
- |
- |
- |
11.4 |
12.6 |
- |
| Sulfidity, % on AA |
62.5 |
73.6 |
62.5 |
62.5 |
62.5 |
62.8 |
| 2nd EA @ 5 min, % NaOH |
2 |
2 |
2 |
- |
- |
2 |
| Residual EA, g/L Na2O |
13.6 |
22.0 |
14.4 |
15.9 |
15.7 |
|
| Resid. polysulfide, g/L S° |
1.6 |
1.6 |
|
1.9 |
2.6 |
- |
| |
| COCURRENT STAGE: |
|
|
|
|
|
|
| Total time, min |
61 |
60 |
60 |
73 |
75 |
60 |
| Max temperature, °C |
164 |
165 |
164 |
170 |
170 |
165 |
| Time at max, min |
45 |
45 |
45 |
45 |
45 |
45 |
| EA, % NaOH |
5 |
5 |
6 |
- |
- |
5 |
| EA, % Na2O |
- |
- |
- |
4.75 |
5.25 |
- |
| Sulfidity, % |
0 |
0 |
0 |
0 |
0 |
0 |
| Residual EA, g/L Na2O |
8.5 |
14.0 |
8.0 |
10.2 |
9.6 |
|
| |
| COCURRENT STAGE II: |
|
|
|
|
|
|
| Time, min. |
- |
- |
|
135 |
72 |
- |
| Temperature, °C |
- |
- |
|
170 |
170 |
- |
| EA, % Na2O |
- |
- |
|
2.85 |
3.15 |
- |
| Sulfidity, % |
- |
- |
|
0 |
0 |
- |
| |
| COUNTERCURRENT STAGE: |
|
|
|
|
|
|
| Time, min |
240 |
240 |
240 |
- |
- |
240 |
| Temperature, °C |
164 |
160 |
164 |
- |
- |
165 |
| EA, % NaOH on wood |
15.3 |
15.4 |
15.4 |
- |
- |
15.4 |
| Sulfidity, % |
0 |
0 |
0 |
- |
- |
0 |
| EA, g/L as NaOH |
11.9 |
12.0 |
12.0 |
- |
- |
12.0 |
| Displacement, L/min. |
0.16 |
0.16 |
0.16 |
- |
- |
0.16 |
| Displaced volume, L |
38.4 |
38.4 |
38.4 |
- |
- |
38.4 |
| Displacement Residual : |
|
|
|
|
|
|
| @ 60 minutes, EA g/L Na2O |
6.9 |
10.4 |
|
- |
- |
|
| @ 120 minutes, EA g/L Na2O |
7.6 |
9.1 |
|
- |
- |
|
| Total Composite, EA g/L Na2O |
7.3 |
9.6 |
|
- |
- |
|
| |
| END OF COOKING: |
|
|
|
|
|
|
| Residual EA, g/L NaOH |
10.0 |
10.0 |
|
12.4 |
13.4 |
|
| g/L Na2O |
7.7 |
7.8 |
|
9.6 |
10.4 |
|
| H factor |
2733 |
2239 |
2695 |
2947 |
1935 |
|
| |
| UNBLEACHED PULP: |
|
|
|
|
|
|
| Total yield, % |
45.5 |
44.6 |
|
43.5 |
45.6 |
|
| Rejects, % |
0.02 |
<0.01 |
|
<0.01 |
<0.02 |
|
| Screened yield, % |
45.5 |
44.6 |
|
43.5 |
45.6 |
|
| Kappa, unscreened |
17.1 |
12.4 |
15.1 |
11.7 |
15.6 |
|
| Kappa, screened |
16.9 |
12.6 |
|
11.7 |
14.6 |
|
| Kappa, screened (test 2) |
16.8 |
12.4 |
|
11.7 |
14.4 |
|
| Viscosity, 0.5% CED, cp |
42.4 |
33.7 |
|
23.6 |
32.3 |
|
| Viscosity, (test 2) |
43.7 |
34.5 |
|
22.0 |
32.4 |
|
| V/K, (test 1) |
2.51 |
2.67 |
|
2.02 |
2.21 |
|
[0037] As can be seen from the above examples, the method according to the invention optimizes
the viscosity/kappa ratio and/or strength properties of kraft pulp produced, and achieves
other advantageous results. The utilization of polysulfide or elemental sulfur as
part of the sulfide content of the white liquor also significantly increases yield.
[0038] When using other lignin reaction enhancing or carbohydrate degradation slowing chemicals,
such as anthraquinone or its derivatives or equivalents, or the like, significant
increases in viscosity/kappa ratio or pulp strength properties can be obtained by
targeting one cooking liquor to a specific stage (or stages) of the cook, while another
cooking liquor is used in other portions.