U.S. patent number 3,830,688 [Application Number 05/334,785] was granted by the patent office on 1974-08-20 for method of reducing the discharge of waste products from pulp mills.
This patent grant is currently assigned to Skogsagarnas Industri Aktiebolag. Invention is credited to Nils Viktor Mannbro.
United States Patent |
3,830,688 |
Mannbro |
August 20, 1974 |
METHOD OF REDUCING THE DISCHARGE OF WASTE PRODUCTS FROM PULP
MILLS
Abstract
Method for reducing the amount of waste products discharged from
cellulose pulp mills to limit the pollution of recipient water into
which the wastes are finally discharged. The amounts of coarse pulp
waste products as well as fines which pass the dewatering wire
cloths are reduced in a single treatment stage, while sulphides and
resin acids with black liquor residues left in the pulp are
chlorinated and/or oxidized before they are discharged into the
recipient water. The volume of waste water is kept small. The
process is characterized by the omission of the conventional washed
unbleached pulp screening operation and passage of the unbleached
pulp and wash medium directly to the bleaching operation. The
unbleached pulp washing step is performed with aqueous supplanter,
e.g., white water or vapor condensate, and is to be distinguished
from fresh water washing.
Inventors: |
Mannbro; Nils Viktor (Morrum,
SW) |
Assignee: |
Skogsagarnas Industri
Aktiebolag (Vaxjo, SW)
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Family
ID: |
26769222 |
Appl.
No.: |
05/334,785 |
Filed: |
February 22, 1973 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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83371 |
Oct 23, 1970 |
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654998 |
Jun 21, 1967 |
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Current U.S.
Class: |
162/29; 8/156;
162/60; 162/66; 162/88; 162/55; 162/65; 162/78 |
Current CPC
Class: |
D21C
11/04 (20130101); D21C 9/02 (20130101) |
Current International
Class: |
D21C
11/04 (20060101); D21C 9/00 (20060101); D21C
9/02 (20060101); D21C 11/00 (20060101); D21c
009/02 (); D21c 009/08 (); D21c 011/00 () |
Field of
Search: |
;162/17,31,41,51,89,60,65-67,78,88,87,55,96 ;8/108,109,111,156 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
rydholm, "Pulping Processes," Interscience Publishers, (1965), p.
839..
|
Primary Examiner: Bashore; S. Leon
Assistant Examiner: D'Andrea, Jr.; Alfred
Attorney, Agent or Firm: Brooks Haidt & Haffner
Parent Case Text
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of applicant's prior
copending application, Ser. No. 83,371, filed Oct. 23, 1970 now
abandoned, which bears the same title, and which was a
continuation-in-part of application Ser. No. 654,998, filed July
21, 1967 now abandoned.
Claims
Having described my invention, what I claim is:
1. A method of reducing fresh water requirements and the discharge
of solid and liquid wastes from mills producing bleached pulp from
ligno-cellulosic material, by non-oxidative digestion of the major
part of the lignin and then by oxidative bleaching of the
cellulosic residue wherein solid material which was incompletely
digested in converted into useful cellulose pulp and screening
wastes while simultaneously alleviating the malodorous and toxic
character of composite wastes comprising digestion effluents and
discharged solid wastes, including fines in white water, and
limiting the BOD of such composite wastes, comprising the steps
of:
a. passing the solid residue of the ligno-cellulosic material and
spent liquor mixture from a pulp mill digestion stage directly to a
brown stock washing step using a liquid aqueous supplanter
containing BOD-increasing volatile digestion residues from spent
liquor evaporation condensate that is recycled for the recovery of
the spent digestion chemicals from the pulp and, to render the
brown stock suitably free of original spent liquor;
b. passing the brown stock and any spent liquor entrained thereby
along with incompletely digested solid material, from the brown
stock washing step directly to an oxidation stage of a bleaching
plant utilizing the brown stock consistency from the final brown
stock washing stage, and subjecting said brown stock, incompletely
digested solid material and entrained liquor as well as remaining
BOD-increasing aqueous supplanter to the oxidizing action of an
accordingly increased charge of bleaching chemicals selected from
the group consisting of oxygen, peroxides, chlorine dioxide and
chlorine for the simultaneous bleaching of the pulp, oxidative
delignification of incompletely digested material and oxidation of
spent liquor chemicals including resins and other toxic or
BOD-increasing digestion products;
c. increasing the yield of useful bleached cellulose fibre and to
the same extent reducing the polluting discharge comprising coarse
solid waste material by converting the incompletely digested coarse
material to useful cellulose pulp in the simultaneous waste
alleviation and fibre liberating delignification of the oxidation
step (b), into which step all fines material with BOD is contained
and oxidized before any fraction thereof can escape with a reduced
volume of deodorized white water either to a pulp mill effluent
purifying plant for fibre recovery or to recipient water; and
d. passing the material from step (b) to a bleach plant alkaline
extraction and washing stage supplied with liquid aqueous
supplanter, for extraction of the aqueous solubilized
chemicals-pregnant discharge from said oxidation stage.
2. A method according to claim 1 wherein a fraction of incompletely
converted material passing from the oxidation step (b) is separated
by immediate screening of pulp in suspension with the aqueous
solubilized chemicals-pregnant discharge and then added to the
brown stock and returned therewith to the oxidation step with an
additional amount of the oxidizing chemical for repeated fibre
liberating delignification, thereby reducing the discharge of
oxidized waste materials and further increasing the yield of
finally bleached cellulose fibre.
3. A method according to claim 1 wherein sodium compounds are used
with oxygen in step (b), producing an aqueous extraction discharge
from step (d), said chemicals-pregnant discharge containing
alkaline solubilized oxidation products, and including passing said
sodium compounds to a digestion liquor regeneration process.
4. A method according to claim 1 in which the pulp manufacturing
process is the sulphate process and pulp-entrained black liquor
containing toxic and malodorous sulphide compounds from the brown
stock washing step (a) is recovered to a digestion liquor
regeneration process as a component of the discharge of step
(d).
5. A method according to claim 1 when chlorinating chemicals are
selected for oxidation in step (b) wherein an amount of the
chlorinating oxidizer is consumed in addition to the demand of the
actual pulp bleaching and wherein chlorine dioxide replaces
chlorine to achieve high efficiency oxidation of black liquor and
vapor condensate residues which are extractable by water, while the
transport of aqueous solubilized chemicals-pregnant and
incompletely digested material to the subsequent alkaline
extraction washing stage is adjusted by recovery of solubilized
products containing alkaline filtrate with only small amounts of
chlorine compounds to a digestion chemicals regeneration process by
supplanting residual black liquor from the brown stock in step (a)
with said alkaline filtrate from step (d) and then with vapor
condensate and a chlorinating stage effluent.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a method of reducing the amount of waste
products discharged from cellulose pulp mills, for the purpose of
reducing pollution of the recipient water into which such waste
products are discharged.
2. Description of the Prior Art
With rapid industrial growth and increasing population densities
throughout the world, pollution of rivers, lakes and streams has
become a very serious problem. One of the contributors to this
contamination has been cellulose pulp mills which normally dump
very large volumes of contaminated effluent water into recipient
rivers, lakes and streams. It is a principal object of this
invention to decrease the amount of waste products discharged from
pulp mills.
The usual conventional process of sulphate pulping and bleaching
has been described by Casey, in his book Pulp and Paper, which
deals with brown stock washing in Chapter IV and with waste
disposal in Chapter IX. In such a prior art process, pulp and black
liquor from sulphate wood digestion pass on to a pulp washer for
black liquor displacement. The diluted black liquor is passed to a
regeneration plant. The washing cleans the pulp as thoroughly as
possible of black liquor. The pulp, along with some remaining black
liquor, is diluted with large quantities of water in a stock chest,
producing a diffusion of sulphides, resins and other black liquor
components.
The diluted pulp stock is screened and the screened pulp goes to a
water extractor. The screened pulp passing to the extractor is
accompanied by all of the dissolved waste products. The extracted
waste water seriously contaminates the recipient body of water, for
example a stream, river or lake. In ordinary processing as set
forth the volume of waste water from unbleached pulp screening
amounts to about 50 cubic meters per ton of pulp. The biochemical
oxygen demand (BOD) of the wastes can be between 15-25 kg BOD per
ton of pulp, that is, about 0.25 kg. BOD per kg of solids. The
solids are, of course, dissolved wood substances derived from the
black liquor which was entrained by the pulp stock since the pulp
washing stage.
Not only do such wastes increase the BOD load on the recipient
water, but also some of the waste components are poisonous. The
undesirable results of such a process are particularly pronounced
if the foul black liquor evaporation condensate is passed directly
to the pulp washing stage undiluted by the addition of fresh
water.
The waste water from the extractor also contains fines or
Noll-fibres, which pass through the de-watering wirecloths of the
extractor in an unbleached state. These fines also contribute to
the BOD load on the recipient. Screening rejects from conventional
processes, that is, incompletely delignified material, represent a
further solid waste disposal problem.
Also considered by Casey, cited above, is the conventional
bleaching process for pulp. The pulp obtained from the water
extractor as described above passes next to a bleaching operation.
Bleaching is usually carried out in a multistage process, starting
with an initial bleaching step using one of the common oxidizing
agents, e.g. chlorine, hypochlorite, chlorine dioxide, oxygen or
peroxide. If chlorine is used, the chlorination products must be
dealt with, and these include chlorinated phenol compounds.
It is standard procedure in prior art multistage bleaching systems
to wash the pulp between the several oxidizing bleaching stages and
to solubilize the residual products of the initial oxidizing stage
by alkaline extraction followed by washing with water. White liquor
may be used for this treatment step. In oxidizing bleaching 5
percent to 10 percent NaOH is used simultaneously with the oxygen,
and the alkaline pulp stock resulting from the oxygen bleaching is
extracted under alkaline conditions by washing with water
alone.
The subsequent conventional bleaching stages are well known to
those skilled in the art. The bleach plant effluents contribute
further to the BOD load resulting from the wastes in the previously
extracted water. The total waste liquids to be disposed of after
conventional sulphate pulping and bleaching is about 200 m.sup.3 to
300 m.sup.3 of waste liquids per ton of pulp. Depending on the
particular type of bleaching and the kind of pulp treated, the BOD
of the bleaching effluents is usually between 5-10 kg per ton of
pulp, but this load may be as great as 20 kg/ton pulp. Adding the
BOD of the bleaching effluents to the BOD of the extracted waste
water, the total BOD has usually been over 40 kg/ton of pulp in
prior art plants.
Attempts have been made to reduce the waste water volume and the
BOD by in-process effluent recycling and the use of the alkali
content of alkaline bleaching effluents in the pulp digestion
process, e.g. for washing unbleached pulp prior to its screening.
Products released from alkaline stage can, however, only be
introduced to the cooking liquor regeneration process if the alkali
is pure, i.e., contaminated only with a very small amount of
chlorine compounds.
It is a common practice to treat the waste water in settling ponds,
whose surfaces release foul gases, mainly originating from the
sulphidic wastes. The ponds are often aerated to lower the BOD, but
vast volumes of waste water are involved.
The weight of organic substances contained in the spent liquor
obtained when digesting either sulphite or sulphate pulp is
approximately equal to the weight of the recovered pulp. The
sulphite pulp industry has caused serious water pollution problems.
These problems have become less serious where combustion of
sulphite spent liquor has been established as an economically
acceptable process. With regard to water pollution, the sulphate
pulp industry has had a much more favorable starting point. The use
of relatively expensive but easily regenerable cooking chemicals
explains the successful development of the recovery process for the
manufacture of sulphate pulp. The complete success of the sulphate
process has been limited in that low concentrations of foul
smelling substances are discharged in the form of gases to the
atmosphere, and toxic substances to the sewage water and recipient
water.
The spent sulphate digestion liquor (or so called black liquor)
obtained during the digestion of sulphate pulp contains resin acids
which are poisonous to fish and other animal life. Sulphides and
mercaptans are also poisonous per se and also spoil surviving fish
by imparting to them an unappetizing flavour and taste.
All of these compounds may cause serious damage even though they
only appear in the recipient water in concentration of only a few
milligrams per liter of water.
To assess the poison activity of sulphides and sodium salts of
resin and fatty acids a more exhaustive study must be conducted,
but as has been mentioned, the poison activity of the sulphides can
be reduced by chlorinating the entire volume of water obtained when
screening the unbleached pulp. Solid waste is separated from the
screens at this stage of the process i.e., subsequent to washing
and prior to bleaching. This solid waste presents a problem;
whether it be flushed out into the recipient water or deposited on
land. The screening of pulp from the digester is primarily intended
to remove such solid waste as incompletely delignified wood chips,
shives and bark residues and other constituents which resist fiber
liberation by cooking and subsequent bleaching. These fractions are
obtained as reject from screens and hydro-cyclone cleaners. If the
rejects cannot be marketed as coarse pulp or e.g., utilized in the
production of packaging materials, they represent a serious
disposal problem.
A significant step forward has already been taken by removing
coarse, unpulped material and knots before the pulp is washed and
screened, these being returned with their black liquor content to
the digestion step. After re-cooking a significant portion of the
reject material will be accepted by screening. Re-cooking may,
however, lead to a fraction of the acceptable material having
relatively poor bleaching properties or increased consumption of
bleaching chemicals.
Other disposal methods involve burning the waste either in
incinerators or, suitably after shredding, together with black
liquor in a soda recovery furnace. The deciding factor may, in
certain cases, depend upon the value of the alkali remaining in the
reject.
In some instances it is even considered to be industrially most
economic to use knots and screen rejects for ground levelling.
In the foregoing there has been discussed the conditions for
treating sulphate pulping waste, containing so-called knot pulp and
screen rejects, sulphides with pulp from digestors and soap with
resin acids as the most deleterious components in the black liquor
loss. The present invention is based upon a study of how these
constituents of the waste can be treated.
SUMMARY OF THE INVENTION
It has been found that the said constituents should not be treated
individually, as has previously been the case, but that the waste
should be subjected in its entirety to one common treatment. It has
also been found that the treatment can be effected with no adverse
effects on the quality characteristics of the bleached pulp. The
invention provides a great advantage in modern methods for
continuous digestion in direct connection with the washing of the
pulp, where there has been a desire to effect screening in less
space-demanding screening departments with small fresh water
requirements. Quite simply, the invention improves measures
previously applied only in successive, separate treatment stages in
a novel, efficient and comprehensive method with a novel effect, to
completely or partially eliminate the following large groups of
waste products:
1. incompletely digested material
2. poisonous products from the digestion operation
3. dissolved wood substances which increase the oxygen demand of
the recipient
4. fines in white water from thickeners and filters for screened,
unbleached pulp.
The method of the invention has the following advantageous
features:
1. The quantity of waste water and, to the same extent, the need
for fresh water is reduced in that the entire screening procedure
for washed unbleached pulp is omitted.
2. Equipment for black liquor recovery by washing the pulp is
dimensioned so that all water used in one form or other for the
final, clean washing of the pulp is utilized in counter current
flow to the pulp and finally passed to the evaporation plant,
instead of loading the recipient water with unbleached pulp
screening white water.
3. Unbleaced pulp from the last washing stage filter and/or press
for recovering liquor is passed directly to the first stage of the
subsequent bleaching operation, where oxidation and/or chlorination
agents react with the sulphide sulphur compounds and extracted
substances of the pulp and liquor residues entrained therewith, at
a concentration of said agents that is required for pulp
bleaching.
4. Oxidation or chlorination products of sulphides and liquor
residues present in aqueous solutions are extracted from the pulp
while coarse material which has been delignified to some extent is
subject, either directly or indirectly, to further processing.
5. Pulp from an alkaline bleaching stage is diluted with water
recycled from the same or later alkaline stages, and is separated
from the incompletely delignified material by means of suitable
screen arrangements, cyclone cleaners and other separating
means.
6. The fraction of incompletely delignified material separated
according to item 5 above is mixed with the flow of unbleached pulp
to the first bleaching stage. Preferably this material is first
defibered in refiners and/or screened to remove constituents
unsuitable for mixing with the flow to the first stage; these
screening rejects are substantially free of sulphide sulphur
compounds as compared to their composition when still present in
the unbleached pulp.
7. In the continuous state of operation there is added to the
initial bleaching stage an additional amount of oxidation agents,
chlorine or other such substances, corresponding to the
requirements for delignification of returned pulp and oxidation of
poisonous sulphide sulphur compounds or black liquor residuals as
well as conversion of extractives from pertinent wood species.
The novel method according to the invention provides, in one single
treatment stage, a reduction of the coarse pulp of the waste
products as well as fines which pass the de-watering wirecloths,
while sulphides and resin acids with black liquor residuals left in
the pulp are chlorinated and/or oxidized before they are released
to the recipient water, in a relatively small volume of waste
water. The elimination of the screening of unbleached pulp causes a
reduction of the requirements for fresh water in the plant, which
may be of critical importance for expanding plants. (In certain
instances sea water may be used in the bleaching plant up to the
last washing stage, including also screening of the alkaline pulp
suspension between the bleaching stages according to the present
invention.)
For conventional screening the washed unbleached pulp is diluted.
This step must be followed by corresponding thickening by water
removal before bleaching can be effected. This dewatering process
is accompanied by a loss of a fine fraction of fibres. If these
fines are permitted as such to accompany the waste water into the
recipient they add considerably to the load of the said recipient.
This load is reduced if all pulp, without being subjected to
losses, is passed to the introductory bleaching stage. Losses of
delignified fibre from filters and thickeners subsequent to
screening between bleaching stages cannot, on the other hand, be
entirely avoided but they can easily be either recovered or
rendered harmless by treating the relatively small volume of waste
water that is released from the bleaching plant only. Naturally,
the same amount of lost fibres imply a lower BOD after
delignification with oxidation agents such as chlorine compounds,
and elimination of the sulphide sulphur contents of the pulp which
the lost fibres originate from.
Sedimentation ponds, filters and other purifying plants, and pipe
lines and distributing means in the recipient need only be
dimensioned for waste water from the bleaching department and
subsequent treatment of the pulp. Foul smelling gases are often
given off from surfaces of waste water in sedimentation ponds or
settlers. According to the present invention such sulphide-sulphur
compounds are eliminated, and as a result thereof also such
hydrogen sulphide formation which takes place when waste water,
containing sulphide containing liquor, is mixed with acidic waste
from, inter alia, pulp bleaching stages. The more uniform and more
concentrated the recovered fibre material the greater are the
possibilities of usefully utilizing the same. The total volume of
waste water for an average number of more modern sulphate plants
which include bleaching plants is between approximately 200 and 300
m.sup.3 per ton pulp. Of this the waste water from the screening of
washed, unbleached pulp comprises 50 to 100 m.sup.3 per ton
pulp.
To render harmless sulphides and other poisonous sulphur compounds
and resin acids together with other extractive substances from the
liquor, a threshold value for the concentration of chlorine or
other oxidation agents in the waste water must be passed. It is,
therefore, important to work with the least possible volume of
waste water. The present invention is therefore more favorable than
chlorination or aeration of the excess of white water from
thickeners and filters for unbleached pulp.
The practical performance of the described method is influenced by
economic conditions concerning increased consumption of chlorine or
chlorine compounds and other oxidation agents in the initial
bleaching stage. The unpulped material from the digestion consumes
more bleaching agent than the average pulp but, subsequent to
delignification in the first bleaching stage, will result in an
increased yield of liberated fibre. The value of the increased
yield of pulp contributes to complete or partial compensation for
the increased cost in chemicals for treating the waste water.
Further, when manufacturing sulphate pulp it is possible to provide
an optimal relationship between firstly, the return to the digester
of the coarse fraction of the undigested material which is removed
from the suspension of black liquor and pulp before the final
washing stage and, secondly, bleaching of the remaining undigested
material after it has passed the pulp washing department. Thus, the
redigestion of screening rejects would finely divide non-desired
material which cannot be bleached in a conventional system, but
which according to the invention is liberated and separated by
means of screening between bleaching stages.
To reduce the quantity of chlorine consuming constituents and black
liquor present in the fibre after normal filter washing, the brown
stock washing plant can include a diffusion stage before bleaching
and preferably prior to the final washing stage or the pressing
stage. Washing in continuous digesters and diffusers and similar
washing apparatus give, in this respect, a better result than
filter washers. Batch washing in diffusers can also be effected to
advantage by means of the present invention.
Chlorination is normally effected at a pulp consistency of
approximately 3 percent. It is therefore necessary to dilute, if
the pulp from the washing filters with a consistency of
approximately between 10 and 15 percent is to be chlorinated under
normal conditions. Preferably, dilution can be effected with return
water, e.g. from chlorine dioxide stages, in a manner known per se,
with vapour condensate containing sulphide sulphur components.
Other processes use such high pulp concentrations, e.g. of about 20
percent to 60 percent as in U.S. Pat. No. 3,251,730, that fluffed
pulp is treated with chlorine and/or chlorine dioxide gas. In the
case of gas phase oxidation, the present invention affords the
additional advantage that the relatively high pulp concentration
from the last washing stage, filter or press, is utilized for
pressing prior to fluffing. Gas phase chlorination is also
particularly suited for unscreened pulp containing coarse,
un-delignified material from the digester stage. Certain effects of
a more penetrating delignification conducted in gas phase have also
been noticed on coarser material subjected to redigestion, when it
has been separated prior to the washing operation for the recovery
of black liquor.
Modified sulphate digesting processes have been developed in latter
years. One such process is digesting with liquor containing
significant amounts of polysulphide. Another process utilizes
substantially only sodium sulphide. These processes result in
higher concentrations of sulphide and organic sulphur compounds in
the products which accompany the pulp. In conventional washing and
screening of such pulps the release of sulphides into the recipient
must therefore be increased. This is counteracted by moving the
screening stage to a position in the bleaching sequence according
to the present invention. The vapour condensate from these modified
pulping processes contains more sulphide sulphur than does the
conventional sulphate process condensate. Therefore condensate from
the evaporation stage, and to a certain extent from the digestion
stage, should be used for washing the pulp. If the condensate in
the washing stage is not supplanted with fresh water sulphidic
sulphur compounds follow the pulp from the filter, and thus not
only is the discharge of deleterious substances into the recipient
increased but also the odor level in the screening department. Thus
the direct bleaching of the washed pulp according to the invention
also presents obvious advantages in this respect. It provides for
simultaneous discharge of black liquor losses and water-soluble
chlorinating and oxidating products. Even though the total effect
is favorable, chlorinated phenol compounds have certain poisonous
effects. Chlorine dioxide may also in this respect favorably
replace chlorine in the first bleaching stage. If chlorine dioxide
is used in the application of the present invention, the black
liquor and condensate residuals, containing sulphur and other
compounds, entrained with the pulp will be oxidized at higher
efficiency than when using chlorine. In this instance the invention
can with the same advantage be applied to both sulphite and
sulphate pulp bleaching. Irrespective of whether the invention is
applied by using chlorine, hypochlorite, or chlorine dioxide in the
first bleaching stage, the transport of reaction products to the
subsequent alkaline stage is increased as compared to the
conventional bleaching of pre-screened pulp.
Products released from the alkali stage can only be processed in
the cooking liquor regeneration system if the recovered alkali
contains small amounts of chlorine compounds. This is achieved with
chlorine dioxide which, after all, has five times as great
oxidative effect per chlorine atom. Thus, the present invention
affords a particularly high effect if applied with chlorine dioxide
in the first bleaching stage and with the recovery of filtrate from
subsequent alkaline pulp extraction stages. This filtrate will also
contain residues of products released during the digestion stage.
Recovery can be effected by utilizing the alkaline filtrate for
preparation of cooking liquor or be introduced in the waste liquor
via the pulp washing stage. When washing sulphate pulp on filters
the filtrate can be sprayed onto the pulp web to displace or
supplant residual black liquor. Remaining alkaline filtrate is
supplanted or displaced with water, either in the form of newly
added water or in the form of vapour condensate or reuse of washing
water from the process. The water employed can accordingly be
called a "supplanter" or "displacing medium." The method can in
itself contribute to a more effective washing out of sulphidic
black liquor if the filtrate from the bleaching stage is free of
sulphide. The amount of chlorine or oxidation agents introduced to
the introductory bleaching stage can be reduced if the pulp is
washed in the most effective manner possible.
The conditions are somewhat different if white liquor or possibly
soda liquor (green liquor) is used in the alkaline stages of the
bleaching department. The advantage of this process is that in this
form the alkali is less expensive than in caustic liquor. It may be
more expedient for pulp digestion purposes to utilize caustic
liquor if sulphite is included in the cooking liquor. The
disadvantage with white liquor for bleaching purposes is primarily
that chlorine consuming sulphide residues accompany the alkali
extracted and washed pulp to the next bleaching stage. Further, the
risk of hydrogen sulphide formation must also be taken into
account.
When filtrate from alkaline stages from the bleaching sequence
contains sulphide it is still more important, from the aspect of
water conservation, to recover the filtrate. If such filtrate is
taken into the liquor regenerating process via the unbleached pulp
washing this should suitably be undertaken before the last washing
stage so that the first bleaching stage is not unnecessarily
loaded.
The present invention is particularly effective in the case of the
oxidation of sulphide e.g., introduced by vapour condensate, in the
alkaline bleaching filtrate, which is used for recovering black
liquor in later stages of the pulp washing prior to bleaching.
Conventionally, the residual sulphide should follow the unbleached
screening waste water to the recipient but, according to the
present invention, these residuals are oxidized in the initial
bleaching stage.
Methods for complete recovery of chlorine-containing bleach plant
waste water are not yet available in actual practice. To obtain,
according to the invention, an almost complete unloading of the
recipient it is necessary to use oxidation agents in the initial
bleaching stage, which enables the introduction of the washed-out
reaction products into the cooking liquor (white liquor)
regenerating process of the pulp plant. Suitable oxidation agents
from this aspect are peroxide and air or oxygen, at suitable
temperatures and pressure ratio. In the latter case catalysts may
also be used. In latter years interest, inter alia, has increased
in the use of initial bleaching stages with oxygen and alkali,
accompanied by suitable bleaching sequences wherein chlorine,
chlorine dioxide and alkali are included. In this way high
brightness sulphite and sulphate pulps, having good quality
characteristics in general can be produced. Since a fibre
liberating delignification process takes place in the first
bleaching stage the pulp can be screened directly. The present
invention can therefore be adapted so that the otherwise less
effective oxidation (aeration) of the waste water rather is
operated as an optimated bleaching stage with recovery of alkali
together with the oxidation products. A further advantage with
regard to the quality of the pulp is obtained in that oxidation
prevents the formation of chlorinated extractive substances. These
chlorination products are, in hardwood pulps, often insoluble in
subsequent alkali stages and therefore reduce the brightness
stability of the bleached pulp.
The alkaline necessary for alkaline oxidation with oxygen can be
added at the last washing filter for waste liquor recovery, or in
connection with the last washing stage. Certain pulp lignin
oxidation processes use significant amounts of alkali in the order
of up to 5 or 10 percent NaOH calculated on the pulp. If the alkali
balance of the pulp plant is upset thereby, regenerated liquor
should be used for the bleaching process. In certain other
processes for alkaline treatment of pulp, sulphur compounds in, for
instance, white liquor have been found to protect against
cellulosic decomposition. In the present instance oxidization to
sulphate takes place at high temperatures. If the said alkaline
bleaching waste liquor is to be used for digestion purposes with
sulphite in the cooking liquor it is more advantageous to have
converted sulphide and thiosulphate by oxidization.
BRIEF DESCRIPTION OF THE DRAWING
The drawing shows a system for performing the method of the
invention in schematic form.
DESCRIPTION OF A PREFERRED EMBODIMENT
The drawing illustrates a system adapted for the performance of the
method of the invention. The reference character 1 denotes a
continuous digester having a washing zone 1a. A conduit 2 leads
from the zone 1a of the digester 1 to a brown stock washing plant
3. A pipe 4 for returning black liquor also connects the brown
stock washing plant 3 and the digester 1.
The pipe 5 leads from the digester 1 to an evaporation plant
schematically shown at 6.
An outlet line 8 of the brown stock washing plant 3 leads to a
bleaching unit 9, which is preferably for the initial bleaching
stage of a series of successive bleaching stages (not illustrated).
An oxygen feed line to the bleaching unit 9 is shown at 10, and a
feed line for alkali is shown at 11.
The oxidation products of the initial bleaching stage leave the
unit 9 through a conduit 12, travelling to a screen arrangement 13,
whence screening rejects leave at 14 to pass to a refiner 15. The
refiner 15 is connected to the bleaching unit 9 for recycling of
refine screening rejects.
Line 16 carries screened stock to a filter 17 fed with vapor
condensate at 18 and water as shown at 18a. Conduit 19 for filtrate
branches into a line 20 leading back to a cooking liquor
regeneration plant 21 (shown in dashed lines), and also into a
branch to line 7 leading back to the brown stock washing plant
3.
The conduit 22 carries regenerated cooking from the plant 21 to the
digester 1.
The right hand end of the figure of the drawing shows a conduit 23
leading to a subsequent bleaching unit 24. Although only one unit
24 is illustrated, there would preferably be a series of such
units. The outlet 25 is for bleached pulp and the final recipient
of wastes is shown at 26.
The method of the invention will be more clearly understood from
the following example:
EXAMPLE
Wood was digested according to the sulphate process with an
alkaline cooking liquor containing sulphide. The digestion was
carried out in a continuous digester 1 and in cooperation with a
washing of the pulp at a zone 1a of the digester 1. The digestion
products comprised pulp and incompletely digested wood such as
knots, as well as black liquor. The products were passed through a
conduit 2 to a brown stock washing plant 3 for final washing of the
pulp stock. Black liquor from washing was passed in counter-current
flow to the pulp through a pipe 4 to the digester 1 and was then
introduced through pipe 5 to the evaporation plant 6. Washing was
accomplished by adding washing water partly comprising evaporation
condensate through the pipe 7. This evaporation condensate
contained sulphides and mercaptans of which a fraction added to
other BOD and toxic components of the black liquor residue at the
outlet 8 from the washing plant 3. The washed pulp stock was
transferred directly to the initial stage, at 9, in a series of
successive bleaching stages, thereby avoiding the dilution in the
waste water producing pulp screening procedure which is
characteristic of previously known pulp treatment methods.
The fines accompanying the pulp as well as the diffusible soap and
other potential contaminants all flowed along with the pulp stock
up to the oxidizing bleaching treatment stage. The initial
bleaching stage at 9 comprised treatment with oxygen fed in at 10
and with alkali shown entering at 11, the alkali containing a
residue of sulphide emanating from the cooking liquor recovery
process. A catalyst was also added. For pulp delignification, 6
percent NaOH, calculated on pulp at a suitable temperature and
pressure ratio, was used. Simultaneously incompletely digested
materials, i.e., knots, were subjected to a fibre-liberating
delignification to form useful cellulose pulp, while the various
BOD and toxic components were oxidized.
The initial bleaching stage oxidation products were discharged at
12 and treated in an arrangement of screens 13. After oxidation any
remaining liberated material was separated as screening reject and
left the screens at 14 to be treated in a refiner 15 prior to
mixing the pulp entering the first bleaching stage 9 through the
conduit 8.
The screened stock passed from the screen as shown at 16 to be
treated on a filter 17 using vapor condensate introduced at 18 and
some water shown entering at 18a to supplant the oxidation spent
liquor. The filtrate removed at 19 contained not only comsumed
alkali added for bleaching, but also alkaline compounds released
with the digested pulp. Recovery of the alkali value was
accomplished by passing a first part of the filtrate through the
conduit 7 to the washing plant 3 for washing digested pulp while a
second part of the filtrate flowed as shown at 20 to be used in the
preparation of cooking liquor at the plant 21. Dilution for
screening was provided for by recycling filtrate to the screens 13
as shown at 19b.
Alkali was introduced at 11 to the oxygen-alkali bleaching stage 9.
The alkali was supplied by the cooking liquor regeneration plant
21, which also supplied regenerated cooking liquor to the digester
1 through a conduit 22. By this means the alkali balance of the
entire pulp plant was controlled.
The stock containing delignified and washed pulp and remaining
condensate was conveyed through the conduit 23 to a subsequent
bleaching stage 24 with bleaching agents of high oxidizing power
such as chlorine and chlorine dioxide. The bleached pulp finally
was removed at 25 and treated by conventional means. The waste
products discharged from the final bleaching and treatments, e.g.
delignified and bleached fines, had relatively low BOD and
contained no sulphidic sulphur compounds. The waste water
containing these wastes, and leaving the mill at 26, was free from
foul smelling substances. The total volume of waste water
discharged by the sulphate mill was cut to approximately 100 cubic
meters or less per metric ton of bleached pulp.
It will be understood that brown stock washing, after digestion and
before bleaching according to the invention, provides for washing
of the pulp and the return of cooking chemicals to the digestion
stage, before the pulp is passed on for bleaching. The washing is
accomplished with "supplanter" or "displacing medium" -- water
which has been recycled or added. This arrangement separates the
digestion from the bleaching stages, but allows the fines, and
other incompletely digested solid materials, toxic materials, etc.
to be subjected to the oxidizing action of bleaching chemicals
along with the pulp before the pulp is separated from such
materials as are to be discharged to a waste recipient.
Various modifications and substitutions falling within the spirit
and scope of this invention will suggest themselves to those
skilled in the art of pulp process. The example stated above is
merely intended as a non-limiting illustration of a preferred
embodiment.
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