U.S. patent number 3,878,037 [Application Number 05/374,839] was granted by the patent office on 1975-04-15 for method of enhancing the hypochlorite bleaching of pulp.
This patent grant is currently assigned to Betz Laboratories, Inc.. Invention is credited to Philip S. Davis, Gerald D. Hansen, Elizabeth G. Varney.
United States Patent |
3,878,037 |
Hansen , et al. |
April 15, 1975 |
Method of enhancing the hypochlorite bleaching of pulp
Abstract
The present invention is directed to pulp bleaching processes,
and in particular compositions for use in the bleaching process to
enhance the efficiency of the process. It was discovered that if a
low molecular weight water soluble polymer of acrylic acid, or
water soluble salt thereof was added either alone or together with
a carboxymethyl cellulose to the bleaching solution, that less
bleaching solution was required.
Inventors: |
Hansen; Gerald D. (Holicong,
PA), Varney; Elizabeth G. (Levittown, PA), Davis; Philip
S. (Furlong, PA) |
Assignee: |
Betz Laboratories, Inc.
(Trevose, PA)
|
Family
ID: |
23478394 |
Appl.
No.: |
05/374,839 |
Filed: |
June 29, 1973 |
Current U.S.
Class: |
162/73; 162/87;
252/187.26; 162/76; 252/187.29 |
Current CPC
Class: |
D21C
9/1036 (20130101) |
Current International
Class: |
D21C
9/10 (20060101); D21c 003/04 (); D21c 003/18 () |
Field of
Search: |
;162/72,75,76,87,73
;252/95,187H ;8/108 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Bashore; S. Leon
Assistant Examiner: Alvo; M. Steven
Attorney, Agent or Firm: Ricci; Alexander D.
Claims
Having thus described the invention what is claimed is:
1. A method of enhancing the hypochlorite bleaching of pulp which
comprises adding to the bleaching medium, a water soluble
polyacrylic acid homopolymer or its water soluble salt, said
homopolymer having a molecular weight of from about 500 to 20,000
and contacting said medium with an aqueous slurry of the pulp to be
bleached, said homopolymer being added to the bleaching medium in
an amount of from 0.5 to 100 parts per million parts of aqueous
slurry pulp.
2. A method according to claim 1 wherein calcium hypochlorite or
sodium hypochlorite is used to bleach the pulp.
3. A method according to claim 1 wherein a water soluble
carboxymethyl cellulose is used in conjunction with the
homopolymer.
4. A method according to claim 3 wherein the homopolymer and
carboxymethyl cellulose are used in a weight ratio of homopolymer
to cellulose of 12:1 to 1:12.
5. A method according to claim 4 wherein the combination of
homopolymer and methyl cellulose are added to the pulp slurry in an
amount of from about 0.5 to 100 parts per million.
6. A method according to claim 1 wherein the homopolymer of acrylic
acid is sodium polyacrylate having a molecular weight of 1000.
Description
BACKGROUND OF THE INVENTION
The bleaching of wood pulp to obtain lighter grades of pulp to
produce corresponding lighter or whiter grades of paper finds its
origin long into the past as indicated by U.S. Pat. No. 11,343
(July 18, 1854).
Since this time many advances have been made in the processes,
however modern methods still utilize chlorination, caustic
extraction to dissolve chlorinated lignins, and final hypochlorite
bleaching in one or more stages.
The theory of reactions occurring in chlorination and hypochlorite
bleaching of alkaline pulps for example is described quite
comprehensively in Chapters II and IV of "The Bleaching of Pulp"
Tappi Monograph Series No-10. Basically calcium and sodium
hypochlorite solutions have been utilized for the bleaching of pulp
which for the most part require alkaline solutions.
As is well-known, different grades of paper require different
degrees of brightness of the pulp. In order to obtain the
brightness level desired, the pulp has a certain demand of calcium
or sodium hypochlorite (commonly referred to as "hypo") to perform
the function desired to in turn produce the desired brightness
level. These parameters are well defined by the mill personnel only
because of comprehensive testing and experience. Accordingly for a
desired brightness for a certain pulp, mill personnel can quite
accurately estimate the conditions of bleaching required together
with the hypo demand. The overall costs of the bleaching operation
even if only the costs of the bleaching chemicals are considered,
is quite substantial. Accordingly mills look favorably upon any
additives or procedural innovations which can lessen these costs to
any degree.
It was to this objective that the present inventors directed their
attention. The present inventors felt that if the bleaching
reaction could be controlled relative to the rate of reaction that
perhaps greater bleaching efficiency could be obtained. It was
discovered that if a low molecular weight water soluble polymer of
acrylic acid (or water soluble salt) was added to the hypo
solution, that the rate of reaction in fact was controlled so as to
provide what was believed to be a slower bleaching cycle, or slower
reaction rate thereby permitting a smoother, more even, and
accordingly a more effective bleaching operation. Because of these
achievements, less hypo was required to obtain a prescribed
brightness value. This represented a cost savings which obviously
was quite impressive to bleaching operations' personnel. Treatments
using from about 0.5 to 100, and preferably from 1.0 to 50 parts
per million parts of pulp slurry were found to be quite effective.
Although the polymers described have been found to be suitable for
the purpose when used alone, the preferred treatment is a
combination of the polymer with carboxymethyl cellulose (or water
soluble salt thereof and preferably the sodium salt) in a weight
ratio of from 12:1 to 1:12 polymer to methylcellulose with the
preferable ratio being 10:1 to 1:6. The desired treatment range
with the combination was also 0.5 to 100 ppm of pulp slurry and
preferably 1.0 to 50 ppm.
SPECIFICS OF THE INVENTION
The inventors tested the concept of extending the oxidative life
(bleaching life) by studying the oxidation-reduction potential of
treated and untreated reaction solutions. By choosing an
established reaction, the amount of time necessary to reach various
stages of the "oxidation-reduction potential" of the reaction could
be measured. The objective of course was to extend the life of the
oxidation and to avoid the formation of non-oxidizing
(non-bleaching) reaction products.
In order to develop this information the following test was
conducted with the results thereof being recorded in Table 1. The
product used was of the following composition in the percentage by
weight composition specified.
Example 1 ______________________________________ 14.85% -- sodium
polyacrylate (molecular weight 1000) 1.50% -- sodium carboxymethyl
cellulose 0.15% -- cationic surfactant (Hyamine 3500) 83.50% --
water ______________________________________
The reduction of a solution of sodium hypochlorite by sodium
thiosulfate was followed with an oxidation reduction couple using a
glass electrode and a platinium electrode. In order to calculate
the real oxidation-reduction potential in a system where pH could
vary, the pH was measured a number of times throughout the
reduction cycle.
For purposes of the laboratory investigation, 1 ml of the sodium
hypo solution was added to 200 ml of deionized water and titrated
with an 0.1 N thiosulfate solution.
In the treated systems, 1.0 ml of the sodium hypo solution was
added to 190 ml of deionized water. 10 ml of an 0.1 M solution of
calcium nitrate solution together with 1 ml of product of Example
1--10.sup.4 ppm was also added.
The plots of ORP vs time for the addition of 2 ml of the
thiosulfate solution were made. The important aspects of such are
tabulated in the following Table 1.
Table 1 ______________________________________ Time to reach
Treatment 75% 50% of initial ORP
______________________________________ None 30 seconds 7 minutes
Product of Example 1 14 minutes 25 minutes
______________________________________
Conclusions
The length of time to reach the limiting ORP was greatly increased
in the treated samples, and the rate of initial reduction was
slower in the treated samples.
The effect of this activity on the bleaching of pulp is thought to
be two fold:
1. a slower rate prevents uneven attach on the residual lignin and
results in a lower bleach consumption to attain a desired
brightness, and
2. the lower rate of reduction limits the formation of chlorate ion
in the bleach liquor, which is a non-bleaching ion in this
environment.
Mill-Trails
In order to establish the in-field efficacy of the product, a plant
trial was conducted using the Product of Example 1. The mill which
was located in the State of Washington, was bleaching a fir pulp.
The desired brightness according to the mills' scale was 84GE. The
Product was added directly to the calcium hypochlorite bleach
solution in an amount 18 parts per million parts of pulp slurry.
The Product's efficacy was compared to the efficacy of the
commercial product currently being used by the mill.
The comparative results are set forth in thee following Table.
Table 2 ______________________________________ Objective: 84GE Fir
Treatment Days of lbs/ton of hypo Treatment required to produce
objective ______________________________________ Commercial Product
(over period used) 34.0 Product of Example 1 1-6 29.9 Product of
Example 1 7-14 28.5 (Dosage increased to 20 ppm) Commercial Product
15-22 34.1 Later date Commercial Product 1-24 31.4 Product of
Example 1 25-48 28.7 Average hypo requirement: Commercial
Product=33.2 lb/ton Product of Example 1=29.0 lb/ton
______________________________________ Reduction in hypo demand
with the use of Product of Example 1 = 12.65% Therefore 4.2 lb/ton
reduction = 14 gallons per ton realized or 42 cents/ton saving.
A second trial was conducted at a mill located in Wisconsin. This
mill also used calcium hypochlorite as the bleaching agent and
averaged 170 tons/day of pulp bleached.
The mill utilized a "hypo factor" procedure in determining the
amount of bleaching necessary to obtain a given brightness of pulp.
The mill's criteria was as follows:
0.1 hypo factor = 1 gal/ton
Normal factor = 2.1 to obtain a given brightness
With the addition of 1/2 lb/ton of the Product of Example 1 to the
hypo solution, the hypo factor was 1.7 which represented a
substantial decrease in hypo demand.
Likewise when 1/4 lb/ton of the Product of Example 1 was added to
the hypo, the hypo factor was 1.8.
When the feed of the Product of Example 1 was discontinued, the
hypo factor rose to 2.0 and subsequently increased to 2.1 to obtain
the necessary brightness.
The mill trials substantially confirmed the conclusions derived
from the laboratory studies, and clearly substantiated the
effectiveness of the product.
* * * * *