U.S. patent number 3,632,469 [Application Number 04/830,709] was granted by the patent office on 1972-01-04 for process for the manufacture of dissolving grade pulp.
This patent grant is currently assigned to Ethyl Corporation. Invention is credited to Harry D. Wilder.
United States Patent |
3,632,469 |
Wilder |
* January 4, 1972 |
**Please see images for:
( Certificate of Correction ) ** |
PROCESS FOR THE MANUFACTURE OF DISSOLVING GRADE PULP
Abstract
A process for the production of a dissolving-grade pulp in high
yield by removing lignin and hemicellulose from chips of fibrous
plants by refining the chips, delignifying the refined matter with
chlorine dioxide, and removing the hemicellulose with acid
prehydrolysis and strong caustic extraction.
Inventors: |
Wilder; Harry D. (Richmond,
VA) |
Assignee: |
Ethyl Corporation (New York,
NY)
|
[*] Notice: |
The portion of the term of this patent
subsequent to July 6, 1988 has been disclaimed. |
Family
ID: |
27125388 |
Appl.
No.: |
04/830,709 |
Filed: |
June 5, 1969 |
Current U.S.
Class: |
162/25; 162/66;
162/89; 162/60; 162/67 |
Current CPC
Class: |
D21C
9/142 (20130101) |
Current International
Class: |
D21C
9/14 (20060101); D21C 9/10 (20060101); D21c
009/14 () |
Field of
Search: |
;162/66,67,88,89,25,60 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
wise et al. Wood Chemistry 2nd Edition Reinhold Pub. Corp. 1952 p.
267 .
Rydholm Pulping Processes Interscience Pub. 1965 pp. 1071 to
1074.
|
Primary Examiner: Bashore; S. Leon
Assistant Examiner: Scavone; Thomas G.
Claims
1. A process for producing a highly polymerized dissolving-grade
pulp from vegetable matter in a yield of at least about 45 percent
by weight, based upon the dry weight of said vegetable matter, by
removing lignin and hemicellulose from said vegetable matter, said
process comprising, in combination, the steps of:
a. pretreating said vegetable matter to obtain a refined vegetable
matter in a yield of about 64 percent to about 100 percent by
weight, based upon the dry weight of said vegetable matter;
b. reacting said refined vegetable matter with a lignin reaction
agent selected from the group consisting of chlorine dioxide,
solution of chlorine dioxide and water, and mixtures of chlorine
dioxide and chlorine; and
c. extracting the reaction products and said hemicellulose of
said
2. The process of claim 1 wherein said pretreating is a chemical
prepulping selected from the group consisting of alkafide
prepulping, acid sulfite prepulping, cold soda prepulping, soda
prepulping, sodium xylene sulfonate prepulping, polysulfide
prepulping, bisulfite prepulping, kraft
3. A process for producing a highly polymerized dissolving-grade
pulp from vegetable matter in a yield of at least about 45 percent
by weight, based upon the dry weight of said vegetable matter, by
removing lignin and hemicellulose from said vegetable matter, said
process comprising, in combination, the steps of:
a. subjecting said vegetable matter to acid prehydrolysis;
b. pretreating said vegetable matter to obtain a refined vegetable
matter in a yield of about 64 percent to about 100 percent by
weight, based upon the dry weight of said vegetable matter;
c. water washing said refined vegetable matter;
d. reacting said washed vegetable matter with about
eight-fifteenths of at least about 1 percent to about 15 percent of
a chlorine dioxide lignin reaction agent, based upon the total
weight of dry fibrous material fed to said pretreating stage until
said agent is substantially consumed;
e. water washing said treated vegetable matter;
f. treating said washed vegetable matter with approximately 4
percent by weight water-soluble caustic material based on the dry
weight of said vegetable matter entering step (f) for at least
about one-half hour at a temperature of from about 50.degree. C. to
about 75.degree. C., said treating being carried out at from about
5 percent to about 50 percent pulp consistency;
g. water washing said treated vegetable matter;
h. reacting said washed vegetable matter with about one-half the
amount of chlorine dioxide lignin reaction agent used in step (d)
for about 30 minutes to about 4 hours at a temperature of from
about 40.degree. C. to about 60.degree. C.
i. water washing said vegetable matter;
j. treating said washed vegetable matter with approximately 4
percent by weight water-soluble caustic material based upon the dry
weight of said vegetable matter entering step (j) for at least
about one-half hour at a temperature of from about 50.degree. C. to
about 75.degree. C., said treating being carried out at from about
5 percent to about 50 percent pulp consistency;
k. water washing said vegetable matter;
l. reacting said washed vegetable matter with about one-half the
amount of chlorine dioxide lignin reaction agent used in step (h)
for about 2 to about 6 hours at a temperature of from about
40.degree. C. to about 80.degree. C.
m. water washing said vegetable matter;
n. treating said vegetable matter with a water-soluble caustic
material in aqueous solution at a pulp consistency of about 10
percent for about 1 hour at room temperature, said solution
containing from about 50 to about 60 grams of alkali per liter.
o. press-washing said vegetable matter;
p. reacting said refined vegetable matter with about one-half the
amount of chlorine dioxide lignin reaction agent used in step (l)
for about 2 hours to about 6 hours at a temperature of from about
40.degree. C. to about 80.degree. C.; and
4. The process of claim 3 wherein said chlorine dioxide lignin
reaction agent is selected from the group consisting of chlorine
dioxide, a solution of chlorine dioxide and water, a mixture of
chlorine dioxide and
5. The process of claim 4 wherein said water-soluble caustic
material is
6. The process of claim 4 wherein the pretreatment is substantially
a
7. The process of claim 4 wherein said prehydrolysis is conducted
for from about 10 to about 180 minutes at from about 300.degree. to
about
8. The process of claim 4 wherein said pretreating is a chemical
prepulping selected from the group consisting of alkafide
prepulping, acid sulfite prepulping, cold soda prepulping, soda
prepulping, sodium xylene sulfonate prepulping, polysulfide
prepulping, bisulfite prepulping, kraft
9. The process of claim 8 wherein said neutral sulfite prepulping
comprises contacting said vegetable matter with from about 5
percent to about 30 percent sodium sulfite by weight and from about
3 percent to about 25 percent sodium carbonate by weight, both
percentages being based upon the
10. The process of claim 1 wherein said vegetable matter is
subjected to an
11. The process of claim 10 wherein said prehydrolysis is conducted
for from about 10 to about 180 minutes at from about 300.degree. to
about
13. The process of claim 1 wherein said lignin reaction agent is a
mixture of chlorine dioxide and chlorine and said chlorine is less
than about 30 percent by weight of the total chlorine dioxide
requirement on an
14. The process of claim 1 wherein the pretreatment is
substantially a
15. The process of claim 2 wherein said neutral sulfite prepulping
comprises contacting said vegetable matter with from about 5
percent to about 30 percent sodium sulfite by weight and from about
3 percent to about 25 percent sodium carbonate by weight, both
percentages being based
16. The process of claim 1 wherein the pretreatment is followed,
sequentially, by water washing, chlorine dioxide treatment, water
washing, dilute sodium hydroxide extraction, water washing,
chlorine dioxide treatment, water washing, dilute sodium hydroxide
extraction, water washing, chlorine dioxide treatment, water
washing, strong sodium hydroxide extraction, press-wash treatment,
chlorine dioxide treatment, final washing.
Description
BACKGROUND OF THE INVENTION
Wood and the stems of other vascular plants such as reed, bamboo,
cane, and the like, which are or can be subjected to pulping, are
composed of several basic parts. In general, such plants are made
up of about 15 to 30 percent lignins and extractives, such as
resins and the like, with the remainder of the about 70 to 80
percent being carbohydrates. The carbohydrate portion is about 10
to 30 percent hemicellulose with the remainder being cellulose, and
the cellulose portion of the carbohydrate is about 45 to 55 percent
alpha-cellulose and about 5 percent other celluloses.
One of the first steps in converting chips of such fibrous plants
to pulp is to loosen and disintegrate the material structure by
removing most of the lignins therefrom and separating the remaining
carbohydrate fibers into individual fibers. In all known pulping
processes, such as kraft, sulfite and others, when efforts are made
through rigorous conditions to remove substantially all of the
lignin from the fiber mass, the remaining cellulose fibers are
chemically and/or mechanically damaged. This results in a
significant loss of yield and a major reduction in product
molecular weight or degree of polymerization. On the other hand,
use of milder conditions to avoid fiber damage results in retention
of both lignin and hemicellulose, which cannot be tolerated in
dissolving-grade pulps. Thus, the present invention is directed to
removing substantially all of the lignin and hemicellulose while
minimizing cellulose loss and chemical degradation.
SUMMARY OF THE INVENTION
This invention is directed toward a new and novel pulping process
and the dissolving-grade pulp resulting therefrom. The pulp process
removes substantially only lignins, extractives, and hemicellulose
from fibrous plant materials and leaves the cellulose part of the
material substantially undamaged, thereby resulting in
dissolving-grade pulp having new and unusual properties. Since the
pulping process is very selective and substantially only the
lignins, extractives, and hemicellulose are removed, yields are
exceptionally high. The pulping process includes a basic unit of a
chlorine dioxide treatment and alkaline extraction which may be
sequentially repeated, this basic unit being preceded by a chemical
and/or mechanical pretreatment of the fiber chips which may in turn
be preceded by acid prehydrolysis. The last alkaline extraction of
the sequence is stronger than other alkaline extractions (if any)
in order to remove hemicellulose. Each step of the basic sequential
unit is desirably followed by water washing with process liquids
obtained elsewhere in the process, as by countercurrent washing
which has attendant conservation advantages, or with fresh water.
Alkali may also be conserved by similar countercurrent recycle.
A more preferred embodiment of the process is one including an acid
prehydrolysis and a chemical and/or mechanical pretreatment of
prepared fiber chips followed by the sequential processing of the
pretreated chips in a chlorine dioxide treatment, a dilute alkaline
extraction, a chlorine dioxide treatment, a strong alkaline
extraction and a final chlorine dioxide treatment, with each of
these stages being followed by water washing.
An even more preferred embodiment of the process is one in which a
water wash for the final chlorine dioxide treatment is used as the
water wash for the preceding alkaline extraction and so on
countercurrently to the flow of fiber material through the process
to the first water wash following the first chlorine dioxide
treatment; from this point the wash water may then be sent to waste
or treated for recovery of chemicals contained therein.
Another preferred embodiment of the process involves the chemical
pretreatment of prepared fiber chips; the most preferred chemical
pretreatment is a neutral sulfite pretreatment at a specified
concentration of chemicals and cooking cycle.
Yet another preferred embodiment is one wherein the liquid from a
press-wash which follows the strong alkaline extraction stage is
circulated to both the strong and dilute alkaline extractions.
The pulp produced by the process of the present invention has a
higher degree of polymerization, a higher alpha-cellulose content,
a lower resin content, a lower carbonyl content, and a higher yield
than conventionally produced dissolving-grade pulps from the same
wood mixture.
BRIEF DESCRIPTION OF THE DRAWINGS
In the drawings, FIGS. 1 to 4 are block diagrams and FIGS. 5 and 6
are graphs.
FIG. 1 describes the basic process of this invention.
FIG. 2 shows a more preferred embodiment of the process of this
invention, and
FIGS. 3 and 4 disclose highly preferred embodiments of the process
of this invention.
FIG. 5 shows a comparison of pentosan content of the dissolving
pulp with caustic concentration in pulp slurry;
FIG. 6 shows a comparison of average degree of polymerization with
caustic concentration.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to FIG. 1, fiber chips of any fibrous vegetable
matter are fed first to a pretreatment step 10 which may be either
mechanical, chemical or any combinations thereof. If a chemical
pretreatment is used, it is followed by a water wash. Following
pretreatment, the pretreated chips are then fed to a lignin
reaction treatment 11 where they are contacted with either chlorine
dioxide or a mixture of chlorine dioxide and chlorine in either
aqueous solution or as a gas. Following this, the treated material
is preferably washed with water to return the mixture to
substantially neutral pH; then the treated material is subjected to
strong alkaline extraction 12 and again washed with water to return
to substantially neutral pH and to remove the water soluble
materials produced in the extraction step. This produces a pulp in
high yield of good brightness, high degree of polymerization, a
high alpha-cellulose content, a very low resin content, and a very
low carbonyl content.
Referring now to FIG. 2, a more preferred embodiment of the
invention is shown. Prepared vegetable fiber chips are fed to an
acid prehydrolysis 20 and then to pretreatments 21 and 22 where
they are subjected to chemical, mechanical or combined
chemical-mechanical operations to make the lignin, extractives and
hemicellulose more readily available for removal. Following acid
prehydrolysis and pretreatment, the pulp is subjected sequentially
to a lignin reaction treatment 23, dilute alkaline extraction 24,
lignin reaction treatment 25, strong alkaline extraction 26, , and
final lignin reaction treatment 27. Water washing preferably occurs
after the prehydrolysis and chemical pretreatment stages, as well
as after each lignin reaction stage and alkaline extraction
stage.
One of the most preferred embodiments of the invention is shown in
FIG. 3 and includes the sequential steps of first lignin reaction
treatment, dilute alkaline extraction, second lignin reaction
treatment, dilute alkaline extraction, third lignin reaction
treatment, strong alkaline extraction, and fourth lignin reaction
treatment, with a water wash between each step, and having the
first lignin reaction treatment preceded by acid prehydrolysis and
a chemical-mechanical pretreatment. According to this preferred
four-stage lignin reaction treatment, pretreated wood chips (e.g.,
pretreated by acid prehydrolysis, neutral sulfite prepulping, and
mechanical defibration with appropriate intermediate washing
stages) are passed from the first lignin reaction stage 100 into a
first wash stage 101. Water to this stage may be at least partially
made up from countercurrent water from a second wash stage. The
neutralized pulp from the first wash stage is then passed into the
first alkaline extraction 102, which employs a dilute alkali
solution. After the first alkaline extraction, the pulp is
subjected to a second wash in stage 103, water from this stage
likewise being partially fresh and partially furnished by
countercurrent recycle from a third wash stage. From the second
wash stage, the pulp is then passed into a second lignin reaction
stage 104, after which the pulp is again washed in a third wash
stage 105, to which at least a portion of the wash water may be
supplied as effluent from a fourth wash stage. The pulp from the
third wash stage is passed into a second alkaline extraction 106,
which, like the first alkaline extraction is supplied with dilute
alkali. After the second caustic extraction, the pulp is subjected
to a fourth wash stage which again may utilize water from a fifth
wash stage for at least a portion of the required wash water.
Subsequent to the fourth wash, the pulp is subjected to a third
lignin reaction stage 108 and then a fifth wash stage 109 supplied
with partially fresh water and water from final washing in any
desired proportions. From the fifth wash the pulp is subjected to
further alkaline extraction 110 supplied with strong alkali
solution. This stage ensures that a large proportion of the
hemicellulose will be extracted from the pulp to produce
dissolving-grade pulp. From the strong caustic extraction the pulp
is passed through a press-wash, which is more thoroughly described
below with reference to the preferred embodiment shown in FIG. 4.
After the press-wash 111, the pulp is subjected to a fourth and
final lignin reaction stage 112 and then to a final wash 113.
Completely fresh water is supplied to the final wash, and the
washer effluent may be sent to waste disposal or passed
countercurrently to the fifth wash stage and so on as above
explained. Liquid effluent from the press-wash, which contains a
substantial quantity of alkali, is also recycled to the strong
alkaline extraction stage 110 and to the dilute alkaline extraction
stages 106 and 102.
FIG. 4 discloses a preferred embodiment of a press-wash. Pulp from
a lignin reaction stage washer is passed into strong extraction
stage 200 and from there on to pressing stages 201 and 202. Water
from pressing stage 201 is partially recycled to both strong
alkaline extraction stage 200 and prior dilute alkaline extraction
stages. Water from second pressing stage 202 is partially recycled
to the first press, with the remainder being sent to waste
disposal. Pulp from the pressing stages is then passed to a
water-washing stage 203.
The novel process of this invention is suitable for preparing a
novel dissolving-grade pulp from any suitable fibrous vegetable
matter containing lignin. As is necessary with all pulping
processes, the vegetable matter should have extraneous materials
removed before being subjected to the process. For example, in the
case of wood, it must be debarked in a prior operation. In the
following description, wood will be referred to as the fibrous
vegetable material; however, it should be understood that the
process of the invention is applicable to all fibrous vegetable
materials.
Debarked wood, either hard, soft, or mixed hard and soft woods, may
be converted into chips by a Carthage multiknife chipper or other
equivalent apparatus. The chips should be approximately 15 to 75
millimeters in length, 10 to 40 millimeters in width and have a
thickness of 0.5 to 20 millimeters. When chemical or
chemical-mechanical pretreatment is used, it is preferred that
chips have an approximate length and width as described and that
the thickness be from about 2 to about 5 millimeters. Following
chipping, prepared chips are then subjected to the prehydrolysis
and pretreatment steps.
At least two methods are available for reducing the hemicellulose
content of the final dissolving-grade pulp. First, the wood chips
may be subjected to mild acid prehydrolysis prior to the preferred
neutral sulfite pretreatment and mechanical defibration. Such a
stage selectively hydrolyzes the hemicellulose so that is is more
readily removed in subsequent stages. Second, the final extraction
stage in the chlorine dioxide extraction sequence is changed from
the relatively weak extraction used in producing a high-yield
bleach pulp (about 4 percent caustic applied, based on pulp at 12
percent consistency) to a much stronger alkaline extraction. Since
the acid prehydrolysis stage without the strong alkali stage is not
sufficient to remove the required amount of hemicellulose, the
dissolving-pulp sequence includes either the strong alkali stage
alone or both the prehydrolysis and strong alkali stages.
The acid prehydrolysis, when employed, is carried out by charging
the wood to a digester and heating it in the presence of water, the
acidity being entirely developed through reactions in the wood. In
a preferred embodiment, water is added to obtain a ratio of about 4
pounds water per pound of wood, and the mixture is heated to about
340.degree. F. and maintained at this temperature for about 60
minutes when hardwood chips are used as the raw material.
Prehydrolysis is allowed to proceed only to the point where
hemicelluloses are rendered soluble in subsequent treatments, but
the cellulose is not allowed to be degraded or solubilized to an
appreciable extent. The preferred embodiment produces a
prehydrolysis yield of about 88 percent based on hardwood chips
used. More generally, hardwood prehydrolysis is suitably carried
out at a temperature of about 300.degree. to about 280.degree. F.
for a time of about 10 to about 180 minutes; preferably,
prehydrolysis is carried out at a temperature of about 330.degree.
to about 350.degree. F. for a time of about 30 to about 90
minutes.
A mild prehydrolysis is as effective in ultimate pentosan
(hemicellulose) removal as more severe process conditions; the mild
conditions are preferred because of the resultant higher cellulose
retention. Therefore, in cases where very low pentosan content is
essential, the use of a mild water prehydrolysis in the overall
sequence provides the ability to remove the required amount of
pentosans, while maintaining high cellulose yield and most of the
inherently high degree of polymerization.
The hydrolyzed fiber chips are next preferably fed to a
pretreatment step which can be either mechanical, chemical or a
combination of chemical and mechanical. In chemical pretreatment,
the fiber chips are prepulped to a yield at least greater than 64
percent by weight but less than about 95 percent by weight, based
upon the dry weight of the wood chips. In mechanical pretreatment,
which may give higher yields than the 95 percent yield of chemical
pretreatment, the vegetable fiber chips are subjected to a
shredding, refining, or flaking operation, such as is well known in
the art, e.g., by a Pallman knife ring flaker, which by slicing
reduces conventionally sized chips to thin flakes while maintaining
chip length and width, or a standard disc refiner, or the
equivalent. As is also known, the chips may be subjected to water
or steam treatment (in addition to acid prehydrolysis) prior to
flaking or refining, either under vacuum or pressure. Following
either flaking or refining the resulting fibers or fiber bundles
should be as small as possible without significant damage to the
fibers. The optimum size depends upon the flaking or refining
equipment employed as well as on the wood species being treated.
When chemical pretreatment is used, the vegetable fiber chips are
subjected to a chemical treatment followed by a mechanical refining
operation and then a water washing. The chemical pretreatment
results in a yield of at least about 64 percent or greater in the
case of hardwoods and may be a mild prepulping by a neutral
sulfite, nitric acid, kraft or other known pulping process (e.g.,
bisulfite, acid sulfite, cold soda, soda, sodium xylene sulfonate,
polysulfide). A more preferred chemical pretreatment is a mild
neutral sulfite prepulping under particular conditions of chemical
concentrations; the heating and cooking cycles are defined
infra.
The refining step following the chemical pretreatment may be
performed by a standard disc refiner or other equivalent apparatus
and conducted to yield minimum particle size without significant
fiber damage. After either the chemical or mechanical pretreatment
and water wash, a dewatering step may be necessary prior to
subjecting the pretreated fibers to the novel pulping process of
this invention.
It has been found that when using a chemical pretreatment in
preference to only a mechanical pretreatment, the amount of fines
produced in the refining is reduced, the optimum diameter of the
fiber bundles produced is reduced, the energy input to the refining
operation is reduced, the quantity of lignin reaction agent
necessary for pulping to a desired brightness is reduced, the
quality of the final pulp from the novel process is improved, and
the overall yield of the pulp from the final process is in general
increased.
Following acid prehydrolysis and pretreatment, mechanical and/or
chemical, as the case may be, the pulp enters the first lignin
reaction step. In this step, the shredded mass of fiber bundles
resulting from the pretreatment has a consistency of from about 5
percent to about 50 percent by weight, based on the total weight of
shredded mass and water. Chlorine dioxide, if used as an aqueous
solution, may be fed as an approximately 1 percent by weight
aqueous solution, and depending upon the desired concentration of
chlorine dioxide, which is defined infra, additional water may be
added to adjust the mixture to the desired consistency. If gaseous
chlorine dioxide is used, an inert diluent such as air may be
employed to prevent explosion hazards. A mixture of chlorine
dioxide and chlorine may be employed, with the chlorine being less
than about 30 percent by weight of the total chlorine dioxide
requirement on an equivalent oxidant basis.
Any conventional treating tower such as is well known in the art
may be used for the liquid phase chlorine dioxide treatment stage,
and heat may be added, if and as necessary. Also, additional heat
may be supplied to reduce the time of contact between the shredded
mass and the chlorine dioxide, which time is from about 10 minutes
to about 2 hours depending upon the consistency, the temperature,
and the yield of product resulting from the pretreatment step. In
general, the shredded mass of fibers is permitted to remain in
contact with the chlorine dioxide until the chlorine dioxide
charged is substantially consumed. The pH of this system at the
beginning may vary from about 4.0 to about 8.0, and upon
consumption of the chlorine dioxide, the pH of the treated solution
will vary from about 0.5 to about 3.0. Following the chlorine
dioxide treatment, the resulting mass is then water washed in a
conventional vacuum drum washer or the equivalent.
Following the first water washing, and when the material has a
substantially neutral pH, the washed material is subjected to a
first dilute alkaline extraction in a conventional treating tower
such as is well known in the art. In the alkaline extraction, any
water-soluble caustic may be employed, e.g., sodium hydroxide,
potassium hydroxide, ammonium hydroxide, sodium carbonate, ammonia
gas or other or mixtures of these or others; however, an aqueous
solution of sodium hydroxide is preferred. In the extraction, the
alkali application should be approximately 4 percent based on the
oven dry weight of the fibrous material, and sufficient water may
be added or removed to prepare an aqueous fiber mass having a
consistency of from about 5 percent to about 50 percent by weight
based on the total weight of shredded mass present and water. The
alkaline extraction should be continued for at least about one-half
hour at a temperature of from about 50.degree. C. to about
75.degree. C., a preferred temperature being about 65.degree. C.
Following alkaline extraction, the alkali extracted material is
subjected to another water washing under substantially the same
conditions as the first water wash to remove extracted materials
and residual chemicals.
The second lignin reaction may be carried out in a conventional
treating tower such as described for the first lignin reaction
treatment with the desired consistency of material within the tower
being substantially the same for the second lignin reaction as for
the first. Either gaseous chlorine dioxide or an aqueous solution,
approximately 1 percent by weight, may be fed to this second
treatment stage. In this stage the pH is initially from about 4.0
to about 8.0 and finally ends at about 2.0. The lignin reaction is
permitted to continue until substantially all the chlorine dioxide
charged to the treating stage is consumed. The temperature for the
second chlorine dioxide treatment is adjusted to from about
40.degree. C. to about 60.degree. C. to keep contact times to a
minimum of from about 30 minutes to about 4 hours in order to
consume the chlorine dioxide charged. Following the second lignin
reaction, the treated material is subjected to a third water
washing under substantially the same conditions as the first and
second water washings. After the third water wash, a second dilute
alkaline extraction is conducted, followed by a water wash under
substantially the same conditions as the first alkaline extraction
and wash. The washed material at this stage in the process may be
screened, if desired, to remove any shives or fiber bundles which
may remain, these being discarded or returned to the first chlorine
dioxide treatment stage for recycle.
The treated material, whether screened or not, is then subjected to
a third lignin reaction under the same conditions of consistency as
the first and second lignin reaction stages for a period of from
about 2 hours to about 6 hours, depending upon the desired
brightness of product produced. The temperature for this third
lignin reaction treatment stage is from about 40.degree. C. to
about 80.degree. C. Next, the treated material is subjected to a
fifth water wash under the same conditions as the preceding water
washing, followed by a strong alkaline extraction.
Strong alkaline extraction, either alone or in conjunction with a
mild prehydrolysis, is essential for pentosan removal. The amount
of alkali required, and therefore its cost, is significant. For
example, an extraction with 8 percent alkaline solution at 12
percent pulp consistency requires the application of about 1,170
pounds of alkali per ton of pulp on a dry basis. Therefore, it is
important to reduce this value to a minimum both through use of
minimum quantities of applied alkali and through recycle of
extracted liquor. Strong alkaline extraction is carried out at
about 10 percent consistency, and maximum pentosan removal is
accomplished with about 50 to about 60 grams per liter of alkali.
Stronger alkali is not required, but it is important to maintain
the 50 to 60 grams per liter level in the case of hardwoods. The
degree of polymerization level of the alpha-cellulose is not
adversely affected by the alkali. When prehydrolysis is not
employed, maintenance of the desired minimum alkali concentration
is most critical. An intermediate pentosan level is reached at a
much lower alkali application level when prehydrolysis is employed.
If higher levels of pentosan content (4 to 5 percent) can be
tolerated, they can be achieved by either approach; the final
choice depends on the relative economics of a prehydrolysis
compared with the higher alkali requirement when no prehydrolysis
is employed. Since relatively little alkali is actually consumed in
the extraction, recycle may account for about 50 percent of the
total alkali requirement or more. If a low pentosan content must be
maintained, prehydrolysis followed by alkaline extraction with
little recycle is required. Regardless of the number of lignin
reaction stages used, the strong alkaline extraction is used either
before or after the final lignin reaction stage, with the before
case being preferred.
Following the strong alkaline extraction, the pulp is subjected to
a press-water or its equivalent, final lignin reaction treatment,
and final wash under the conditions above described.
The total concentration of chlorine dioxide used in the multistage
process, whether two, three or more chlorine dioxide stages, is
dependent upon the yield of product obtained from the pretreatment
step. In general, the total chlorine dioxide consumed in the
multiple lignin reaction stages, regardless of the number of stages
used, is from about 1.0 to about 15.0 percent by weight based on
the total dry weight of fibrous material being fed to the
pretreatment stage. It has been found and is preferred that the
total concentration of chlorine dioxide used is from about 4.0
percent to about 13.0 percent by weight, based upon the total
weight of dry fibrous material being fed to the pretreatment
stage.
The amount of chlorine dioxide fed to each lignin reaction stage is
dependent upon the number of stages used and on the pretreatment
yield. For any given total amount of chlorine dioxide to be used,
it has been found that approximately two times the amount used in
the last stage should be fed to the stage preceding the last and
two times the amount used in the preceding state fed to the next
preceding stage, and so on. For example, in a three-stage process,
this means that approximately four-sevenths of the total chlorine
dioxide will be fed to the first stage, approximately two-sevenths
of the total chlorine dioxide will be fed to the second stage, and
approximately one-seventh to the third stage. By comparison, in a
four-stage treatment the consecutive amounts employed are
eight-fifteenths, four-fifteenths, two-fifteenths, and
one-fifteenth.
As mentioned previously, the preferred pretreatment for the process
of this invention is a chemical pretreatment, and of the chemical
pretreatments available such as kraft, bisulfite, neutral sulfite,
nitric acid, etc., a neutral sulfite pretreatment is preferred.
And, among the neutral sulfite pretreatments available, a sodium
based neutral sulfite pretreatment is preferred. As well known in
the art, a standard neutral sulfite pulping treatment includes
cooking fibrous vegetable material for a period of about 10 to
about 15 minutes at about 350.degree. F. in a solution containing
approximately 10 percent sodium sulfite and approximately 3 percent
sodium carbonate, chemical charges being based on the wood weight
charged to the process. Although this standard neutral sulfite
pretreatment has advantages, in the process of this invention it is
even more preferred that a specific and novel neutral sulphite
pretreatment be use. This novel chemical pretreatment includes
preparing an aqueous solution with a concentration of from about 5
to about 30 percent sodium sulfite and from about 3 to about 25
percent sodium carbonate (all concentrations based on the weight of
wood present) to provide a sodium sulfite to sodium carbonate ratio
of about 1.2 or greater and using the solution to chemically
pretreat wood chips with or without a prior prehydrolysis step.
More preferred concentrations are from about 7 to about 20 percent
sodium sulfite and from about 5 to about 18 percent sodium
carbonate, all percentages being based upon the dry weight of the
vegetable matter. A preferred sodium sulfite to sodium carbonate
ratio for hardwoods is from about 1.2 to about 1.5. The
time-temperature relationship employed is designed to give adequate
impregnation of liquor into chips prior to reaching a temperature
of about 300.degree. F. This relationship is dependent upon wood
species and chip size, as well as previous chip history. When a
chemical pretreatment is performed in accordance with the described
recipe, higher final yields and higher quality product are obtained
as compared with other mechanical or chemical pretreatments.
The dissolving pulp of the present invention is chemically unique
in that it has a higher degree of polymerization and therefore
greater strength potential than dissolving-grade pulp
conventionally produced from the same wood. For example, average
cellulose molecule size is increased greatly. While the degree of
polymerization (TAPPI Method T-230-Su-66) of conventional
dissolving pulps is less than about 1,000, the dissolving pulp of
the present invention is above 1,000, preferably above 1,500 and
frequently above 2,000, and may extend up to, for example 5,000.
Also, the pulp of this invention has an alpha-cellulose content
(TAPPI Method T-203-OS-61) which is generally greater than 90
percent, frequently greater than 94 percent, and occasionally
greater than 98 percent. The copper number (TAPPI Method
T-215-m-50) of the pulp is generally less than 2.0, frequently less
than 1.0, and occasionally less than 0.2. The resin content (TAPPI
Method T-204-m-54) is generally less than 0.15 percent, frequently
less than 0.1 percent, and occasionally less than 0.05 percent.
Prior art processes give final overall yields, based on wood used,
of 35 to 40 percent, generally closer to 35 percent. The present
invention, by comparison, obtains yields that can be greater than
40 percent, frequently greater than 45 percent, and occasionally
greater than 50 percent, depending upon the process conditions
utilized and quality of pulp required.
Dissolving pulps are used in the alkaline viscose process and the
acidic acetate and nitrate processes to make fibers, yarn, film or
lacquer. In the viscose, acetate, and nitrate processes it is
desirable to have a high alpha cellulose content and a high degree
of polymerization for the production of high-tenacity yarns.
Hemicelluloses have been found to cause decreased reactivity in
both the acetate and viscose processes. In the acid acetate
process, hemicellulose can cause discoloration and haze. This also
indicates the need for a high alpha cellulose content. A low resin
content is desired in dissolving pulps since resin can lead to
clogging and filtering problems as well as haze or undesirable
color in the final product. Since pulps with high carbonyl content
are less stable to aging, a low carbonyl content is desired.
Inasmuch as the pulp produced by the process of the present
invention has a higher degree of polymerization, a higher
alpha-cellulose content, a lower resin content, a lower carbonyl
content, and a higher yield than conventionally produced
dissolving-grade pulps from the same wood mixture, it is well
suited to use in these processes.
The novel process of this invention may be understood better by
reference to the following examples; however, it should be
understood that these examples are intended to be descriptive
rather than restrictive.
EXAMPLE I
Southern hardwood chips are prepared by chipping debarked logs in a
multiblade chipper. These chips are then subjected to a mild
prehydrolysis by heating with sufficient water to give a final
ratio of water to dry wood of about 4 to 1 on a weight basis. The
temperature of the wood-water mass is raised to 340.degree. F. and
held at this temperature for 1 hour. This treatment renders most of
the pentosans soluble in subsequent stages, while maintaining most
of the inherent cellulose yield and degree of polymerization. No
acid other than that generated from wood reactions is present.
The prehydrolyzed chips are dewatered and allowed to soak in fresh
water so the acidic material can diffuse out of the chips. The
chips are then pretreated chemically with a solution containing 12
percent sodium sulfite and 10 percent sodium carbonate, both
percentages based on the incoming weight of dry wood prior to
prehydrolysis. Enough water is added with these chemicals to give a
water to wood ratio of about 4 to 1. Following an impregnation time
of 30 minutes, the temperature is raised to 335.degree. F. and the
pretreatment is allowed to continue until the pretreatment yield
reaches 80 percent.
Following chemical pretreatment, the pressure is relieved (with
accompanying decrease in temperature), free liquid is drained off,
and the pretreated softened chips are passed through a disc refiner
operating at an elevated temperature and pressure. A refiner power
input of 10 horsepower-days per ton of pretreated material is
used.
The defibered material is washed and pressed to the desired solids
level. A maximum of washing is used to minimize the carryover of
chemical to the first chlorine dioxide stage.
The washed, dewatered pulp is mixed with a chlorine dioxide
solution until all chlorine dioxide is consumed. With an 80 percent
pretreatment yield, reaction conditions are 4 percent chlorine
dioxide based on original dry wood, with the reaction proceeding
for 2 hours at ambient temperature. The partially reacted pulp
leaving this stage is washed, 4 percent sodium hydroxide based on
entering fiber is added with sufficient water to give a pulp
consistency of 12 percent, and a 1 hour extraction is carried out
at 60.degree. C. The extracted pulp is thoroughly water washed and
reacted in a second chlorine dioxide stage for 3 hours at 12
percent consistency and 40.degree. C., with an application of 3
percent chlorine dioxide based on starting dry wood.
The further delignified material is washed thoroughly and extracted
for 1 hour at ambient temperature at 12 percent consistency in a
solution containing 60 grams of sodium hydroxide per liter. This
extraction removes partially reacted lignin as well as most of the
pentosans remaining with the pulp.
The purified pulp, still containing small amounts of lignin, is
thoroughly washed until neutral and is then reacted in a final
chlorine dioxide stage for 5 hours at 70.degree. C. and 12 percent
consistency. One percent chlorine dioxide on an original wood basis
is applied in this stage, with essentially complete consumption
occurring during the 5 hour reaction.
Following final washing, a high-grade dissolving pulp is obtained
in a yield of 50 percent, having a pulp pentosan content of 1
percent (TAPPI Method T-223-ts-63), a viscosity average
carbohydrate degree of polymerization of 1,800 (TAPPI Method
T-230-su-66), an alpha-cellulose content of 96 percent (TAPPI
Method T-203-os-61), a copper content of 0.20 (TAPPI Method
T-215-m-50), and a resin content of 0.06 percent (TAPPI Method
T-204-m-54).
EXAMPLE II
The above process is repeated without the prehydrolysis stage to
yield a dissolving pulp of even higher yield (53 percent) and
degree of polymerization (2,300) but having somewhat higher
pentosan content (3 percent).
EXAMPLE III
The following tests were conducted utilizing a mixture of certain
hardwood chips containing approximately one-third oak, one-third
gum, one-third yellow poplar. Acid prehydrolysis was effected by
charging the wood to a digester, adding water to obtain a ratio of
4 pounds water per pound of wood, heating the mixture to
340.degree. F. and maintaining this temperature for 60 minutes.
This produced a prehydrolysis yield of 88 percent. A neutral
sulfite treatment was then carried out, followed by mechanical
refining in an 8-inch laboratory disc refiner and chlorine
dioxide-caustic extraction sequence. Strong caustic extraction was
carried out at 12 percent consistency in an 8 percent solution of
sodium hydroxide. A second pulp was prepared through the same
sequence but without the prehydrolysis stage. The resultant washed
pulps were analyzed for yields, degree of polymerization, and
pentosan (hemicellulose) content, with cellulose yield being
calculated by difference. The results were as follows: ##SPC1##
The above comparison shows that selective pentosan removal without
excessive cellulose degradation can be achieved by optimizing
hydrolysis conditions.
EXAMPLE IV
Five prehydrolysis cooks were carried out under increasingly severe
conditions, again using a hardwood chip raw material. In all cases,
a water to wood ratio of 4.0 was employed, with a 15-minute
digester rise time from ambient to 340.degree. F. The severity was
varied by varying the reaction time at 340.degree. C. Dissolving
pulps were prepared from these prehydrolyzed materials according to
the procedure of example I, the steps including final strong
caustic extraction (8 percent solution). The resulting pulps were
analyzed for yield, pentosan content, and acetyl content. These
values, with assumed typical values for uronic acid and mannan
contents, allowed to the calculation of cellulose yield by
difference. Pulp cuene viscosity was measured, and the values
converted to approximate average degree of polymerization. These
results were as follows: ##SPC2##
The above table shows that mild prehydrolysis is as effective in
ultimate pentosan removal as more severe conditions which result in
a sharp drop in cellulose content. Cellulose degree of
polymerization is little affected by the severity of prehydrolysis.
Mild prehydrolysis does not significantly lower cellulose yield,
does aid in pentosan removal, and results in a significant decrease
in pulp degree of polymerization. Therefore, in cases where low
pentosan content is essential, the use of a mild water
prehydrolysis provides the ability to remove the required amount of
pentosans, while maintaining a high cellulose yield and most of the
inherently high degree of polymerization.
EXAMPLE V
A series of strong sodium hydroxide extractions were carried out at
12 percent pulp consistency using varying levels of alkali
application. The pulp used was prepared by the chlorine dioxide
pulping sequence as described in example I, with and without the
mild prehydrolysis stage. FIG. 5 of the drawings shows the effect
of amount of caustic applied on pulp pentosan content. FIG. 6 shows
the corresponding degree of polymerization changes.
As evident from FIG. 5, maximum pentosan removal is accomplished
with about 60 grams per liter of caustic. Stronger caustic is not
required, but it is important to maintain approximately the 60
grams per liter level. FIG. 6 of the drawings demonstrates that
degree of polymerization was not adversely affected by the strong
caustic extraction. The initial increase in the no-prehydrolysis
case can be attributed to the rather large amount of low degree of
polymerization pentosans being removed.
EXAMPLE VII
Alkali recycle was practiced using the process of example I by
extracting one batch of pulp with strong sodium hydroxide, at 10
percent consistency, squeezing out about one-half of the extraction
liquor (to a pulp consistency of about 18 percent), adding enough
fresh sodium hydroxide to give the desired strength, extracting a
second pulp sample, and repeating this procedure. This amounted to
a fresh makeup of about 50 percent of the total alkali requirement.
Following alkali extraction and thorough washing, pulp pentosan
content was determined. The results are tabulated below for both
the prehydrolysis and no-prehydrolysis cases:
Pentosan Content, % of Pulp Extraction Number No-Prehydrolysis
Prehydrolysis
__________________________________________________________________________
1 4.9 3.1 2 6.5 3.3 3 5.8 5.2 4 6.0 5.5 5 5.7 4.7 6 5.1 4.1
__________________________________________________________________________
From the above data, it is apparent that a significant amount of
recycle can be used and that there is less effect of recycle when
dealing with the nonprehydrolyzed pulps. If a low pentosan content
must be maintained, prehydrolysis followed by extraction with
little recycle is required.
* * * * *