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1
DATF
NOTE BOOK_
PAGE--4 Xk-am.
SIGNED
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/*
Notebook 380 602 AMMONIUM SOLFITE PULPING OBJECTIVE The objective of this project is to investigate the ammonium
896
136-159
sulfite pulping process with emphasis on its application to certain species of hardwoods and the development of a recovery process for the spent cooking liquor.
ATTACK Student pulping data from Course 203 will be used where applicable to provide a foundation for determining cooking conditions. gum, poplar, end oak will be the species pulped. cooking, refining, and testing of the pulps. At present,
RAW MATERIALS
at the Institute in December of 1947 and has been in covered outdoor storage since that time Notebook 818. Data concerning this wood may be found on pages 12-14 in
The poplar was received in January of 1949 and the oak was Both woods
part of a shipment received at the Institute in August of 1948. have been stored out-of-doors since those dates.
dioxide gas and ammonium hydroxide (28.0% solution) dissolved in tap water
FORM 73
EXPERIMENTAL A portion of the gum wood was chipped while still in an unbleached state, and was begged without sorting or screening, batch was barked, chipped to a nominal
3 /4 a
hand sorted and fines which passed a 4-mesh screen were removed. oak bolts were similarly processed
dry wood content was determined by oven drying representative portions of the woods. The digesters used in this study were horizontal, externally heatedbyb means of gas burners. rotary vessels,
and No. 3 digester (stainless steel) were filled with identical wood and liquor charges and cooked simultaneously to provide adequate material for testing
The cooking liquor was made up by adding ammonium hydroxide to cold tap water and sulfiting with sulfur dioxide from a cylinder of compressed gas. It was necessary to cool the liquor makeup vessel with ice to dissipate Sulfiting was continued until the liquor contained
from 75 to 80 g./1. of total S02 as determined by pulping group procedure 2, (Palmrose Method). The concentration of ammonia in the cooking liquor
was determined by distilling an aliquot of the liquor in an excess of sodium hydroxide, using a Kjeldahl apparatus and collecting the distillate in a flask of boric acid solution. The boric acid solution was titrated directly with The ammonia concentration of the liquor
was kept at a point where an additional amount of ammonium hydroxide solution was necessary to bring the chemical input to the required level.
Page 3
The cooked chips from the semi-chemical experiments were defibered in the Bauer pulper using B957 plates. The chips contained warm cooking
liquor when defibered and were diluted with tap water during the process to about 8% consistency.
Washing was affected by draining the defibered stock on muslin-covered wash boxes and replacing the liquor with warm water. the effluent was colorless. Cook 1 was made on unbarked gum.
in Table I.
to be feasible for pulping to a yield of approximately 75%. 74.5% was attained. Cooks 2, 3, and 4 were made on peeled gum chips.
The conditions
for these cooks are also included in Table I. Cook 2 duplicated Cook 1 in all respects except for the raw material, and Cook 3 was the same as Cook 2 except that a longer time at maximum temperature was used Cook 4 was made
in the same manner as Cook 3, but approximately twice as much chemical was used. In the case of Cooks 1 and 2, the contents of the two digesters were
For Cooks 3 and 4, each digester of cooked chips
was kept separate through the defibering, washing, and yielding processes This segregation was undertaken because of very evident differences in the color of the cooked chips from the two vessels. the chips from Digester No. from Digester No. 2. In the case of Cook 2,
TABLE I COOKING CONDITIONS AND PRODUCT VARIABLES AMMONIUM SULPITE PULPING OF GUM AND OAK
Cook No.
Wood used
1
Unbarked Red gum
2A
Peeled Red gum
2B
Peeled Red gum
3A
Peeled Red gum
3B
Peeled Red gum
4A
Peeled Red gum
4B
Peeled Red gum
6A
Peeled Oak
6B
Peeled Oak
13.2
No. 2,3 Rotary 3000
15.9
No. 3
16.1
No. 2
12.8
No. 3
12.4
No. 2
12.8
No. 3
13.0
No. 2
20.5
No. 3
20,5
No, 2
2998
2998
2998
2998
2998
2998
3144
3144
Ammonia basis, O.D..Wood, % so basis, O.D.Wood, % Maximum temperature, C. Maximum pressure, p.s.i.
Time to max. temperature, min.
cc./g.
4.O.
5.0 6.5 176 90
4.0 4.0
5,0 6.5 176 90
5.0 6.5
4.0
5.0 6.5 176 158
90
4.0
5.0 6.5 176
4.0
9.0 13.0
4.0
4.0
10.0 13.0 176
4.0
10.0 13.0 176 160
90
176 90
164
90
162
90
176 155
90
166
90
30 15 74.5 8.0
30 15
135
30 15
135
120 15
225
120 15
225
120 15
225
120 15
225
120 15
225
120 15
225
74.5 8.3
9.6 0.29
67.2 6.2*
1..5 o.45
63.2 8.5
16.8 7.9 13.2
pH
NHE NH g./1. SO3 g./l.
5.6
8.3 Trace
6.5
10.4 005
7.3*
15.7 23.4
9.2 0,21
9.8 0.17
9.4 0.15
16.4 21.4
ll.l
O.21 5
500
0.10
14.1 .. 16
14..1 0.05
14.7 0.13
Clearance,
Load, amps.
*
5
.08 480
5
500
in
08
.008
450
.008
450
.005
350
.005
350
Cook 5 applied most of the conditions used in Cook 4 to poplar chips. Details of this cook and all subsequent cooks on poplar The only variation was that 10% ammonia was used The chips from No. 2 digester were The
darker than those from No. 3 digester, and the pulps were not mixed. aggregate yield from the two digesters was 63.2*
Cook 6 was made using oak chips and the conditions of Cook 50 The cooked chips from the two digesters were not combined because of the darker color of those from Digester No. 2. case was 57-5%. Cook 7 was made on peeled poplar and utilized 15% ammonia and 20% S02. The time at maximum temperature was 4 hours. Because the cooked The yield of pulp in this
chips appeared to be very soft, they were not defibered but were flushed from the digesters with water. mixed. The contents of the two digesters were not
Each of the batches was immediately washed with three changes of During the first and second washes, they were They
were left overnight in the last wash water and then were defibered under the Williams stirrer for 10 minutes, using the TAPPI disc. Screening
took place on the small Valley flat screen, equipped with a .010-inch cut plate. After washing and screening, the color of the pulps were not
The permanganate number of the pulp from No. 2 3 digester was 9.4. The average yield
5
Peeled Poplar
5B
Peeled Poplar
7A
Peeled Poplar
7B
Peeled Poplar
A
Peeled Poplar
B
Peeled Poplar
9A
Peeled Poplar
9B
Peeled Poplar
26.5No.3 Rotary
26.3
No.2
22.7
No.3
23.5
No. 2
23.8
No. 3
22.6
No.2
23.9
No.3
23.7
No.2
2163
4.0 13.0
2163
4.0
2163
4.0
2163
4.0
2163
4.
2163
4.0 00
2163
0
2163
4.0
.
13.0
150
20.0
10
20.0
5 5.0
6.5
5.0
6.5
15.0
20.0
15
20.0
0 Maximum temperature, C
176
146
176
153
176
-
176
-
176
144
176
155
160
118
160
118
Maximum pressure,
ps.i.
Time to maximum temperature, min.. Time at maximum temperature, min. Relief time, min. Total time, cover to dump, min. Unscreened yield, % Permanganate number Black liquor data
90 120 15 225
90 120 15 225
90 240 15 345
90 240 15 345
90 15 105
90 15 105
90 480 15 585
90 480 15 585
65.4
94
5.85
10.7 -
80.7
19.2
651.
21.7
Ph
NH3. g./l. H 4 2 SO3 . g./l. Total solids, % Ash. % Bauer data Feed rate Clearance, i..
Load, amps.
8.6
18.2 18.0 12.7 0.ll 7 o005
250
6.6.
19.3 19.6
8,6
26.2 33.6
7.2*
26.6 46.7 16.9 0.11
7.2
10.5 9.2 605 0.09 5 .005
320
6.2
11.3 11.9 7.6 0.12 5 .005
320
9.25
32.0 27.6 14.3 0.10
6.75
23.5 32.8 17.9 0.13
14.7
0.12 7 .005
250
14.3
0.07
TABLE II
(Continued)
Cook No.
Wood used
Wood moisture content, % Digester used Digester charge, O.D. basis, Ammonia basis,
SO2 basis,
10B
11B
Peeled
Poplar
2163 4.0
5.0
4.0
1000 13.0 158 110
O.D., Wood,
Wood, %
O.D.,
6.5
158 109 90
Maximum temperature, 0 C. Maximum pressure, p.s.i. Time to maximum temperature, min.. Time at maximum temperature, min. Relief time, mine Total time, cover to dump, min. Unscreened yield, % Black liquor data
90
120
120
120
15
225 74.11
15
225
15
225 71.5
15
225
8.9
19.6 18.2
6.4
20.2
8.4
19.6 10.3 0.08
31.3
11.1
0.10
8.7
0.12
in.
.005
420
.005 300
.005 340
8007% was
obtained.
Cook 9 was made in an effort to obtain a well cooked pulp employing
C.
The screened
pulp from digester No. 2 had a permanganate number of 21.7. and that from digester No. 3 was 19.2. The aggregate yield was 65.1%.
Cook 10 was made with a further reduction in maximum temperature to 158 C, The chemical concentration was 5% MH 3 and 6.5% S.2, and the time at The cooked chips were combined before de-
fibering.
70%.
To that end, the conditions of cook 10 were duplicated with the exception that The contents of the two digesters were
Several of the experimental pulps and two commercial poplar pulps were beater evaluated, using Institute Methods 403 and 411, 5500 g. bedplate
loading.The pulp from Cook l was evaluated by making 9-point corrugating medium handsheets and testing these sheets for flat sheet properties and corrugating characteristics. Permanganate number determinations were made as
DISCUSSION OF RESULTS The pulp from Cook 1 was made to provide a comparison of the ammonium sulfite, neutral sodium sulfite, and semi-kraft pulping procedures in the production of semi-chemical pulp for corrugating medium Progress Report 4.
Project 1296 contains data on neutral sodium sulfite and semi-kraft pulps made from the same shipment of gum wood used in these experiments.Table III shows the strength of these pulps as compared with the pulp from Cook 1. It will be
noted that the ammonium sulfite pulp was slightly superior in all strength properties to either the sodium sulfite pulp or the semi-kraft pulps. Beater evaluation data for the peeled gum and oak pulps are shown in Table IV. 7. These data are plotted against beating time in Figures 1 through
Table V compares the physical properties of the pulps at 700 cc. Schopper-
Riegler freeness. From the data in Table V, it can be seen that the pulps from No. 2
and No. 3 digesters in Cook 3 were very similar in strength at 700 cc* freeness. Reference to Figures 2 and 3 indicate considerable variation in strength in the lower freeness levels, with the pulp from No. 2 digester being stronger than that from No. 3. It is felt that the low pH of the black liquor from No. 3 digester had a deleterious effect on the strength of the pulpo The low pH was
probably due to a leak in the digester which permitted the escape of ammonia. Steps were taken to seal the digesters very thoroughly after this experience. In cook No. 4 the strength characteristics of the pulp from No. 3 digester were a great deal higher than those from the No. 2 digester pulp. is not likely that this was due to pH variation. but it may be caused by It
TABLE III FLAT SHEET TESTS AND CORRUGATING STUDY ON GUM PULPS Pulp Identification Cooking procedure
YieldD %
1516-1
Ammonium sulfite 74.5
1296-1 Semi-kraft
75.6 26.
10.2
Flat sheet tests Basis weight, 12x12-1000, lb. Caliper, points Apparent density Bursting strength, points Ring compression, lb. Elmendorf tear, g./sheet Corrugating results Draw Caliper of single-face board, ino H & D flat crush, lb./sq. in.
29.4
10.8
2.7 44 42
100
206 35
23.2
9.9
2.9
41
36.1 91
98
1.56
188 20
1.55
183
18
1.54 183
19
Note:
1. Conditions for corrugating run on 1516-1 are included in Institute file No, 142542 report. 2. Conditions for corrugating runs on 1296-1 and 1296-19 can be found on pages 35 and 36 of Project 1296, Progress Report 4.
Page 11 Project 1516 July 14, 1950 TABLE IV PHYSICAL PEOPERTIES OF GUM AND OAK AMMONIUM SULFITE PULPS Cook Wood used Schopper-Riegl er freeness. cc* 0* 10 2 Peeled Red Gum
3A
Peeled Red Gum
3B Peeled
Red Gum
4B
Peeled Red Gum
6A
Peeled Oak
6B
Peeled Oak
885
875
15 25 30
870 860
750
880
840
835 765
500
170
835
765
495 170
500 165
80
35 45
Basis weight,
385
210
0
10
(25x40)-500,
lbo
15 25 30
46.2 46.4
45.8
47.2
46.5 47.2
46.14 46.4
47.3
45
Caliper, mils.
35
o
10
5.2
4.9
4.3 3.6
5.2
5.0
..7 4.1
.. 6
15 25 30
4.0
35 45
Apparent density
3.8
8.2 8.9
0
10
3.9
9.7 11.4
12.9
15 25 30
10.0
9.5
8.7 9.5
9.4
l0.6
12.8
7,4
9.1
7..8
8.5 9..l
9.9
11.5
10.9
12.6 14.4 16 30
11.2
35 45
Burs t, pt./100 lb.
12.6
14.5
17 25 58
22
0
10
36 61 37
39
23
59
87
35 59 66
28 43 61
28
42
15 25
59
87 91
64
30 35 45
69
76
3B
Peeled Red Gum 1.2 1.4
4A
Peeled Red Gum 1.4
Peeled Red Gum
6A
Peeled Oak
6B
Peeled Oak
Tear factor
0*
10
15 25
1.3
1.5 1.3
1.0
0.5
0.7
1.4
1.0
1.1
1.0
0.6
o.7
0.7
35
45
Tensile, lb./in.
o 0
10
9.5
13.2 21.8 26.1
9.7
15.4
22.0 27.3
15 25
10.7 14.7
21.1
11.9 16.5
21.8
12.5
22.5
16.7
30 35
45
30.0
24.9
24.5 27.5
31.9
TABLE V PHYSICAL PROPERTIES OF GUM AND OAK AMMONIUM SULFITE PULPS AT 700 CC. SCHOPPERE-IEGLER FREENESS Cook Wood species Yield, % Beating time, min. Apparent density Bursting strength, pt./100 lb. Tear factor Schopper tensile, lb./in. 2 Gum 74.5 18 10.4 48 1.2 17.8 3A Gum 67.2 16.5 11.5 65 1.2 22.7 4B Gum 63.2 115 8.3 51 1.0 19.3 6A Oak 57.5 8 10.4 50 0.7 18.3 6B Oak 57.5 8,5 10.6 51 0,7 19.0
25.8
Certainly
the darker color of the pulp from digester No. 2 can be laid to the chemical action on the iron shell.
The pulps from cooks 6A and 6B were alike in all respects.
A comparison of strength properties of peeled gum pulps at various yield levels can be made from the data in Table V. Pulps of 74.5,
67.2, and 63.2% yields show a definite increase in apparent density, bursting and tensile strengths as yield decreased. in tearing strength. yield, Oak ammonium sulfite pulp was low in yield and in all strength properties as compared with cook 4, a gum pulp made with the same cooking conditions used for oak. The results of beater evaluations made on poplar pulps are shown in Table VI and Figures g through 18. A comparison of pulp properties Little change was noted
at 700 cc. Schopper-Riegler freeness is made in Table VII. Reference to Figures 8 and 9 and Table VII indicate some small strength advantage for the pulp from No. 3 digester over that cooked in No. 2 digester in cook 5. About the same increment of superiority is shown for the pulp from No. 3 digester in cooks 9 and 11. In all probability,
the differences in yield between the two digesters could account for the strength variations, since in all cases investigated, the yield of pulp
out of No. 3 digester is less than that from No. 2.
The pulps from cook 5 were much higher in bursting strength than the other poplar pulps, Other strength tests were as good or better
this series. This is particularly
interesting in view of the fact that cook 9 was made with a lower maximum temperature, longer time schedule, and more chemical than used in cook 5,
Probably because of the many changes in variables in this study, it is hard to see any distinct trends in pulp quality at various yield levels when poplar is the raw material. Bursting and tensile strengths appear
to be somewhat higher in the general range of 62 to 72% yield, with decreased strength on either side of this yield level. Tearing strength
seems to be affected comparatively little by yield variations. Four of the ammonium sulfite poplar pulps were analysed chemically, using Institute Methods 421a, 28, 428, and 424a. The results of these
tests are shown in Table VIII, along with an analysis of a kraft poplar pulp from student pulping data from pulping course 203, 1940-41. The data in Table VIII are calculated in terms of percentages of the uncooked wood and listed in Table IX. Also included in this table
are typical data for poplar wood taken from an article by Schwartz and
TABLE VIII CHEMICAL ANALYSIS OF AMMONIUM SULFITE POPLAR PULPS (Basis oven-dry pulp) Cook Yield, Permanganate Alpha number Cellulose, % PentosansD
7
8 9A 9B
201*
58.5
80.7
71.8
0.8
18.4
17.3 20.0 201
57.o
69.4 68.l
13.9 1.5
2.5 3.2
63.2 67.1
52.0
15.9
83.0
16.4
TABLE IX
Pentosans,
18.1*
% Poplar wood
-
number -
Cellulose,% 4.86
% 17.4*
7 8 9A 9B 201**
42,0
10.3 14.0
46.6
43.9 43.2
43.2
12.6
12.7
8.5
Page 38
Project 1516
July 14, 1950
The indications of these data are that the ammonium sulfite process removes lignin more selectively than does the Kraft process, Cook
9B, at 67.1% yield agreed quite well in lignin and alpha cellulose retention with the kraft pulp of 52% yield, but removed less pentosans. Cook 8,
which had a yield of 80.7%, removed the least cellulose, lignin, and pentosans, but it is interesting to note that cook 9A which had a yield
of 63.2%, removed only 2.7% more cellulose and l.4%more pentosans than
cook 8, while reducing the lignin 10.2%. Cook 7, which was more drastic
than cook 9A, indicates that in reducing the yield 4.7% lower than was the case in cook 9A, the cellulose content was reduced 1.9% and the pentosans 1.56 while lignin was reduced only 0.5%. A sample of unbleached poplar sulfite and one of bleached poplar sulfite was obtained from Nekoosa-Edwards Paper Co.
had a permanganate number of 1O.0. It is
physical properties of the unbleached pulp with the pulp from cook 7, which also had a permanganate number of 10.O. Reference to Table VII
shows that the ammonium sulfite pulp beats faster, has a lower apparent density, and higher bursting strength tearing and tensile strength than the acid sulfite pulpo From these data it would appear that the ammonium
sulfite poplar pulp has not only a remarkably high yield as compared with acid sulfite poplar pulp, but is also a stronger pulp.
Page 39 Project 1516 July 14, 1950 ONCLUS IONS The work done to date on ammonium sulfite pulping seems to justify the following conclusions: 1. The ammonium sulfite process gives a corrugating medium
pulp from unbarked red gum that is at least equal in yield and strength characteristics to pulps made from red gum by the neutral sodium sulfite or semi-kraft processes. 2. Ammonium sulfite pulps from peeled red gum are about equal
in strength properties to red gum pulps of the same yield produced by the seni-kraft or neutral sodium sulfite processes. Student pulping course 203, 1947-1948). 3. In the yield range studied, (63.2 to 74.5%), ease of beating and strength properties of gum ammonium sulfite pulps decreased with increasing yield. (The latter data from
southern red oak semi-kraft indicates that this pulp is much stronger than the northern oak ammonium sulfite pulp. 5. Poplar pulped by the ammonium sulfite process showed no
clear cut trend in strength development over a wide range of yields (58.5 to 80.7%). Tearing strength varied little over the entire range
Page 40
6.
periods) did not increase poplar pulp strengths over pulps of similar yield made at high temperatures and short cooking times. ments the reverse seemed to be true. 7 In these experi-
a yield of 58.5% and was stronger in all respects than a sample of commercial poplar acid sulfite pulp. Of note also is the fact that the ammonium sulfite
pulp was more bulky than the acid sulfite pulp. 8. Data from Student pulping course 203 (1947-48) indicates
that semi-kraft poplar pulps in a yield range of 60-65% are as strong as ammonium sulfite pulps in the same yield level. Ammonium sulfite pulps in
the 75% and 78-80% yield ranges were higher in bursting strength but lower in tearing strength than pulps of similar yield made by the semi-kraft process. 9. Data from the same source as indicated in Item 8 show possible
minor strength advantages for neutral sodium sulfite poplar pulps over ammonium sulfite poplar pulps in the yield range investigated by the students. 10. Chemical analysis of ammonium sulfite pulps indicate selective
lignin removal and much less attack on the hemicellulosic fraction of the wood than is experienced in the kraft proces.
Project 1516
11.
General conclusions as to cooking procedures are A. that a tight seal is necessary on the digesters to insure that loss of ammonia will not result in a cook at a low pH. This is important because it is
indicated that high pH is essential to development of maximum pulp brightness and quality. B. iron equipment tends to darken ammonium sulfite pulp and may inhibit cooking
BLEACHING OF AMMONIUM SULFITE PULPS The object of this portion of Project 1516 was to more or less briefly investigate the bleaching properties of a few of the ammonium sulfite pulps described in Project Report One, and to find the effect of bleaching on strength properties.
I1
By referring to Project
Report One it will be found that Cook 4 was made on peeled red gum wood while Cooks 5 and 7 were on peeled poplar. from which the pulp came, the iron rotary. Table I is a repetition of certain data which appears in Project Report One. This table shows the cooking conditions along with yield of the three pulps The "An and "B" identifies the digester
which were later bleached. Because the yields shown on Cooks 4 and 5 are the combined yields of the iron and stainless steel digesters, the conditions used for the B cooks are also shown (although only "A" cooks were bleached). In the
case of Cook 7, however, the pulps from the A and B digester were combined because it was thought that without doing so there would be insufficient quantity for the more extensive work to be performed on this peeled poplar pulp. The combining of these A and B pulps was permissable because of the small difference in the permanganate numbers as shown in Table I.
FORM 73 THE INSTITUTE OF PAPER CHEMISTRY
TABLE I COOKING CONDITIONS AND PRODUCT VARIABLES (Ammonium Sulfite Pulping) Cook No. Wood used Wood moisture content, Digester used Digester charge, O.D. basis, Water ratio, O.D. basis, 4A Peeled Red Gum 4B Peeled Red Gum 5A Peeled Poplar 5B Peeled Poplar 7A Peeled Poplar 7B Peeled Poplar
>
12.8
No.3 Rotary g. 2998
13.0
No. 2 2998
26.5
No. 3 2163
26.3
No. 2 2163
22.7
No. 3 2163
23.5
No. 2 2163
cc./.g.
4.0
9.0 13.0
4.0
9.0 13.0
4.0
10.0 13.0
4.0
10.0 13.0
4.0
15.0 20.0
.. 0
15.0 20.0
Maximum temperature,
C.
176
162 90 120 15 225
176
155 90 90 120 15 225
176
146
176
153 90 90
176
-
176
90
Maximum pressure, p.s.i. Time to maximum temperature, min Time at maximum temperature, min. Relief time, min. Total time cover to dump, min.
120 15 225
120 15 225
240 15 345
240 15 345
Unscreened yield, %
Permanganate number -
63.2
-
65.4
9.4
58.5
10.7
The details on the way these pulps were handled after dumping from the digesters may be found in Project Resort One. In summary, it
might be well to mention here that the pulps of Cooks 4 and 5 were run through the Bauer refiner while the more severely cooked pulp of Cook 7 was merely broken up by means of the Williams stirrer and then screened through the 10-cut screen in the Pulping Laboratory. EQUIPMENT USED The rubber lined pulp laboratory chlorinator of 33 liter maximum capacity was used for all chlorination. This chlorinator is equipped with A rotometer for
measuring the quantity of chlorine gas added to the stock is part of the chlorinating equipment. Subsequent caustic extraction and other stages were Temperature control during bleach-
ing was accomplished by use of water baths in which the crocks were placed. Bleachabilities were performed in quart jars which were placed in a water bath for purpose of temperature control during bleaching. PROCEDURE ANDDISCUSSION Bleaching of Pulp of Cook 4A. The bleaching of pulps of Cooks 4A and 5A was
not done for the purpose of a complete investigation but to get an idea by visual examination of sheets and by brightness tests as to an estimation of the behavior of the fiber towards bleaching.
Page 4 Project 1516 Report No. 2 A 750-gram quantity of the pulp was bleached through chlorination and caustic extraction stages. A portion of this two-staged pulp wa.s next
carried through a calcium hypochlorite third stage and a final sodium chlorite bleach was in turn given a part of this third staged pulp. Table II gives the conditions during bleaching.General Electric brightness sheets were made by Institute Method 412 and these results along with other dataare also given in Table II. The results of tests made on British handsheets from unbeaten Cook 4A pulp bleached as described here, and unbleached pulp as described in Project Report One are given in Table III. This was the extent of the work done on Cook 4A pulp as far as this report is concerned.
exactly the same method as was the pulp of Cook 4A (See Table II), except that a fourth stage was not carried out on Cook 5A, as the color was good and
it was felt that nothing of advantage would be gained by an additional stage at this time. As with Cook 4A, British handsheets were made up on the unbeaten bleached pulp after the third stage. These results are also given in Table
III along with test results on the same pulp before bleaching.
Stage
Pulp Used, cook No. Wood Bleach No. Chlorinati on Pulp charge, g. Consis tency, % Chlorine, O.D. Pulp weight Temperature, O C. Time to apply chlorine, min. Total time, min. Residual Cl2 at dump, g./l.
4A
Gum 1
5A
Poplar
7(A&B) Poplar
7(A&B) Poplar
4
2
750
3
750
3.00
35oo
730 3.00
3.00
22 10.7
basis, %
3.00
22
11.77 30
Trace
11.77 30
10.37
30
Trace
O.142
30 Trace
Caustic Extraction Pulp Charge, g. (all from 1st stage) NaOH, O.D. PULP WEIGHT basis, b Temperature, o C.
Yield through first
Consis tency, %
6.00
6.00 2.50 45
6.00
2.00
6.oo
2.00
50
45
60
60
2 stages,% 91.3
95.8
1280
45 60 95.9
.3
Calcium Hypochlorite Pulp Charge, g. Consistency, % Available chlorine, 0.D. pulp weight basis. % Temperature, Co Time, min, pH range (NaOH used to control pH). Residual swailable o12 at dump,
% of Applied
150
6.00
6.00
4.oo 4.00 44
0.70
35
111
3.0
7.7-9.7
None
30
Yield, start of 3rd stage thru finish,3rd stage, % 60.9 O.E. Brightness Pu Notes: ma ye
99.0
Fiber good white, Few brownishyellow shive
TABLE II (Continued) Pulp Used, Cook No. Wood Bleach No. Sodium Chlorite Pulp Charge, g. Consistency, % Available Chlorine, O.D. pulp weight basis, % Temperature, Time, min. pH C. 4A GUm 1 5A Poplar 2 7(AB) Poplar 7(A&B) Poplar 4
No. 4
70 3.00 005 70
Residual availabl l12 at dump, % of Applied Yield, start of 4th stage thru finish,4th stage, % G. E. Brightness
33.1
65.0
Fiber slightly yellow and some dark shive present
Notes:
Page 7
Project 1516 Report No. 2
TABLE III TEST RESULTS ON UNBEATEN BRITISH HANDSHEETS Cook 4A (Gumwood) Bleached Sheet Weight, g. lbs. 1.3063 46.2 0.00420 24.85 53.5 11.0 Unbleached 1.296 46.1 0.0048 17.8 39 9.4 Cook 5A Bleached .. 3036 46.3 0.00324 43.30 93.7 14 3
First, the bleach requirement of the pulp was found by Institute Method 409. Below is data regarding these bleachability tests: % Available Chlorine Applied Time to Exhaust
5 hr. 50 min..
7.00
6.0
5.0
4 hr. 35 min.
3 hr. 25 min.
77.2
73.0
68.4 62.5
On the basis of the above listed bleachability results it decided to use 30% applied chlorine in the first
was
that this 3.0% figure was more or less picked out of the air;
Page 8
Project 1516
Report No. 2 this were a normal sulfite pulp, probably about 2.05 instead of 3.0. As the capacity of the chlorination is only 1000 grams ovendry pulp basis when chlorinating at chlorine would be applied
3% consistency.
730 grams were chlorinated and caustic extracted separately (Bleach 3 and 4) in order to be certain of sufficient pulp for subsequent work. conditions are given in Table II. After the caustic extraction stage, bleachability tests were run on Bleach 3 pulp under conditions which were to be adhered to in the final bleach. ing time. results. Figure 1 is a plot of chlorine applied versus general Electric brightness as given in Table IV. It was decided to combine the chlorinated and caustic extracted pulps of bleaches 3 and 4 and bleach this whole quantity using 07% available chlorine. The reason the pulps were combined was that it was desired to have General Electric brightness sheets were made at the end of the bleachData on this bleachability test is given in Table IV with brightness The bleaching
sufficient pulp for a beater evaluation after the third stage in addition to enough to give a fourth stage sodium chlorite bleach with a subsequent beater evaluation. From Figure 1 it may be seen that 0.625% available chlorine should
give a brightness of 80.0 to the bleach 3 pulp, but it was decided to use 007$ because a brightness of 80, at least, was the goals The third stage bleach was carried out under the same conditions as the bleachability conditions listed in Table IV. listed in Table II along with yield. These conditions are again
BLEACRABILITY TEST ON CHLORINATED AND CAUSTIC EXTRACTED BLEACH 3 PULP, Cook 7 (M&B) %Availble Chlorine Applied on Pulp Weight Basis 2.00 1.50
1.00 Bleaching Time, min General Electric
Brightness,
84.5
300 300
84.3
84.0
300
102
.50 .25
77.8
70.7
59.0
.25
22
15.0 g. pulp,
O.D. basis
Page 11
Project 1516
Report 2
Four hundred and fifty grams ovendry basis of this third stage combined bleach 3 and 4 was next given a fourth stage bleach with sodium chlorite. Conditions of this bleach are given in Table II. In order to
obtain more efficient use of sodium chlorite chlorine gas in water solution was added to the bleach at the same time the sodium chlorite solution was added The chlorine gas was added in the ratio of one mol of the gas per The pH was lowered before the addition of the
The bleached pulp of Cook 7 was given a beater evaluation after the third stage and after the fourth stage. Valley Beater No, 2 was used
for these evaluations and a bed plate load of 5,500 grams was used Table V gives the results of these beater evaluations along with the results of a beater evaluation made on the Cook 7 pulp before it was bleached, As a test to find the stability of the bleached ammonium sulfite pulp of Cook 7 as to brightness, the General Electric brightness of the
pulps of "Bleachability Tests on Chlorinated and Caustic Extracted Bleach 3 Cook 7 (A&B)" were read on three different days besides the initial day. Following in Table VI is the June 22 reading as given in Table IV plus readings taken on the other three days. The pulps listed in Table VI were washed with distilled water after bleaching and they were not exposed to much daylight as they were stored from June 26 to July 17 in an envelope. for not losing brightness. The conditions thus have been rather ideal
Page 12.
Project 1516
Report 2 TABLE V PHYSICAL CHARACTERISTICS OF UNBLACHED AND LEACHED PULPS OF COOK 7 Pulp Used Bleach number Schopper-Riegler freeness, cc. 0* 10 Cook 7 (A%B) Baw pulp 825 Cook 7(A&B) (3&4)B 3-s taged 810 720 570 390 170 Cook 7(AB)
(3&4) c
810
4-s aged
735 585
390 160
710
520
15 25
330 150
Basis weight,
(25x40-500),lbs.
0 10
15 25
Caliper, mils.
46.5
46.4
46.5
46.5 3.7
3.1 2.9 2.6
3.5
46 5 46.5 3.4
3.2 3.0
2.8
0 10 15 25
3.3
3.2
2.9
2.9 2.8
12.5
5
10
14.0
15.2
13.3
14.5
13.6
14.5
15
25
Bursting strength, pts./100 lbs .0
16.0
17.9
15.9 16.6
15.5 16.6
10 15 25
Tear factor
5S
91
91
74
94 .67
90 93 99 .62 .52
89
75 97
98
10 15 25
Tensile strength, lbs./in00
.58
51 .47 .37
51.5
I
;i
lbs.
5
10 15
66.3
69.6 78.0
65.8
69.6 74.0
Pulp Identification:
General Electric Brightness, % June 22, 1950 June 23, 1950 June26
% Available
Chlorine Applied on Pulp vt. basis
July 17,1950
84.3
1.50 1200 .5O
8l.0
84.5
84.0
0.50 0.25
7708 70.7
76.0
69.9
CONCLUSIONS Table III which gives the results on the tests that we made on British handsheets from the bleached and unbleached pulp of Cooks 4A and 5A gives little information of conclusive value. The bleaching has increased the burst and increased the apparent density. The bleaching, no doubt, removed a large portion of the lignin.
This lignin removal increased the apparent density, and as apparent density at lower freenesses is proportional to bursting strength,
an increase
It is not known if all this increase can be attributed to increase in apparent density and we simply have not enough information to make a statement of fact. Table II shows that after the third stage the brightness of bleached 4A Cook (Gumwood) was 60.9 and bleached 5A Cook (Poplar) was 1g.4. The relative
ease of bleaching of these pulped woods cannot be compared by this data because it may be seen by referring to Table I, that while both woods were cooked with 13.0 sulfur dioxide, the Gumwood was cooked with 9.0% ammonia and the poplar ammonia. The Gumwood was thus given a less drastic cook, and it If the gumwood had been cooked exactly the
with 10.0
have insufficient data to know the answer. The notes under the third stage data in Table II indicate that there was excessive unbleached shive in both the bleached poplar and bleached gumwood. Despite the fact that a high amount of chlorine was consumed in the third stage. 4.0% in each case, the shives were still highly visible. This indicates ammonium
sulfite glumwood and poplar cooked as they were for this work will be difficult to bleach without lowering the cellulose viscosity to considerable amount. It is
possible, however, that the viscosity of the pulp is high after cooking end that the relatively high bleaching chemical that may be necessary will not lower the viscosity to the range where it greatly harms the strength of paper made from the
pulp.
under Bleached Cook 5A pulp in Table III is high for unbeaten pulp and this should encourage more investigation into all the strength properties of bleached
Page 15 Project 1516 Report 2 ammonium sulfite pulps made with chemicals of the approximate strength of this cook (It will be recalled however, that Cooks 4A and 5A were Bauer refined
after cooking and this may have developed the strength.) The bleaching of the Cook 7 pulp was carried out in more detail because it was a more drastic cook than Cooks 4A or 5A and thus more easily
bleachable.
It was stated before in this text that it was desired to obtain a brightness of 80 or greater on the third stage of this bleach. By referring to Table
This indicates
that if further work is done on similar pulp using the procedure outlined herein, to find bleach demand, a brightness of 80 could have been more nearly attained by applying available chlorine that in Figure I gave a brightness of about 82. Probably 0.8%applied chlorine would have given the desired brightness The sodium chlorite 4-th stage bleach was done merely to raise the brightness above 80 with only a small amount of the chemical. a brightness of 82.5 was reached. The Cook 7 bleached pulp did have a few brownish-yellow shive after the third stage, but the sodium chlorite 4-th stage lowered the amount of shive visible to the naked eye to a considerable extent Figure II is a plot of the beating time versus strength test and freeness of the three Cook 7 pulps, that is, unbleached; 3rd staged, and 4th Table II shows
staged, identified as Cooks 7 Bleach(3&4)B; and Bleach (3&4)C. The bursting strength of both the bleached pulps increased to the same degree
Page 16
Project 1516 Report 2 over the unbleached pulp while the tearing strength decreased in both cases but slightly moreso for tensile strength, the sodium chlorite 4th staged pulp. In case of
the 4th staged pulp was about the same as the unbleached but the The freeness curves indicate that the 4th
staged pulp with sodium chlorite was softer than either3d staged with calcium hypochlorite pulp or the unbleached pulp, the latter two being very nearly the
If we refer to Figure III which enables us to compare strength results at constant apparent densities we find that again the bursting strengths for the bleached pulps are about the same and are considerably higher than the bursting strength of the unbleached pulpo The tearing strength shows decreases in both
the bleached pulps with the sodium chlorite bleach showing the greatest decrease, In the case of tensile strength, the bleached pulps both are lower
with the calcium hypochlorite 3rd stage falling off slightly greater than the sodium chlorite 4th staged pulp.
FigureIII shows that increase in bursting strength and the lowering of tensile and tearing strength is not due to differences in apparent densities.
The lowering of tensile and tearing strength may be due to the shortening of the bleached fibers to a greater degree than the unbleached fiber at comparative apparent densities and beating time, and/or it may be due to the lowering of the inherent strength of the fibers due to the action of the bleach.
Ammonium sulfite poplar pulps like other sulfit epoplar pulps have low tensile and tearing strength and these results show that bleaching tends
Page 19
to decrease these particular strength properties. The yields after bleaching of the ammonium sulfite pulps are encouraging, Below is a table showing the results;
Bleaching Yield
56.6 55.5
Cook 5 you may recall was given a mild cook and a drastic bleach while cook 6 was given a more drastic cook and a mild bleach. It thus seems
that a bleached yield of about 55 to 57% can be expected on ammonium sulfite bleached poplar pulps TableVI which gives the brightness variation of Cook 7 ammonium sulfite pulp when 3rd staged with calcium hypochlorite using five different percentages of available chlorine shows that there definitely is some loss. It was thought that ammonium sulfite cooking using an excess of ammonia (high pH, see Project Report 1), would prevent an excessive falling off of brightness, Further study should be made of this critical point to find out if the brightness will continue to fall or if it has reached its minimal It should be stated that the pulp which was beater evaluated seemed to hydrate quite readily. From the beating curve it may be seen that the free-
neas fell very rapidly which indicates low refining costs if the pulp were manufactured on a commercial basis.
With some investigation it may be found that good use could-be made
of bleached ammonium sulfite pulp in glassine, wax, some tissues, and possibly
INTRODUCTIODUT The work covered in this report was divided into two parts. First was
the investigation of possible chemical recovery methods that might conceivably be employed with ammonium base cooking liquors. Efforts to e stablish a chemical
balance from data collected for each of the cooks failed to account for more than about 70% of the nitrogen applied. Cook 12 was therefore made for the
primary purpose of providing data and cooked chips that could be used in investigating the distribution of chemical in chips, black liquor and relief gases.
All of the recovery work done in this study was concentrated on recovery of ammonia. The problem of sulfur recovery, either as sulfur dioxide
EXPERIMENTAL
The following series of experiments were made to determine whether or not a feasible method of chemical recovery could be worked out in the laboratory. There were two general methods employed: (1) precipitation of solids from the A chemical balance was
FORM 73
PRECIPITATION OF BLACK LIQUOR WITH SULFURIC ACID A few test tube experiments showed that acidification of the amnonium sulfite black liquor Produced a precipitate. Accordingly, a 200 ml. sample
of the liouor from Cook 7, containing 26.6 g./l. of ammonia, was acidified with 5K[ sulfuric acid until no additional precipitate formed. After the precipi-
tate had settled, a sample of the supernatant liquor was taken for determination of ammonia. This determination showed the presence of 23.1 g. per liter of
PRECIPITATION BY SULFITITING BLACK LIQOUR An experiment similar to that described above was carried out using sulfur dioxide as the precipitant. In this case, the sample of black liquor The liquor
was taken from Cook 9 and contained 32.0 grams per liter of ammonia.
was sulfited by bubbling sulfur dioxide into the liquor through a gas diffusion disc, then the precipitate was allowed to settle overnight. supernatant liquor showed 31.2 grams per liter of ammonia. A sample of the The liquor was An ammonia
determination after the second sulfiting indicated that the liquor still contained 26.7 grams per liter or a loss of 16.5%; ammonia in the sulfiting process. PRECIPITATION OF SOLIDS BY SULFITING BLACK LIQUOR To determine how much of the suspended solids in the black liquor could be precipitated by addition of sulfur dioxide, the following experimental was performed. A sample of black liquor from Cook 6 was sulfited for 20 minutes
dioxide showed that all the material was not precipitated so the entire sample was resulfited for an additional 15 minutes. After standing overnight, a
A
total solids determination at the same time on the original liquor showed 14.1% solids.
process.
Thus, 5.2; of the solids in the liquor were removed by the sulfiting
PPRECIPITTAION OF AMMONIUM SULFITE BLACK LIQUOR WITH CALCIUM OXIDE Test tube experiments showed that addition of calcium oxide to black liquor resulted in the formation of a slight precipitate. However, the presence
of the lime in the mixture made it difficult to determine how much precipitate was formed. To determine quantitatively the amount of solids removed from the
liquor, a 50 ml. portion of the black liquor from Cook 11 was thoroughly mixed with 3.3 grams of powdered calcium oxide.
made it but it
difficult to detemine whether or not a precipitate was actually formed seemed somewhat doubtful. Heat areasapplied to the mixture and brought During the heating, the liquor
close to the boiling point for several mimutes. foamed with a strong evolution of ammonia.
After cooling
so a portion was centrifuged at about 3,000 RPH for 15 minutes. were determined on the clear liquor as described in the Appendix.
a similar solids determination was made on the original liquor at the same time. These solids determinations showed that the original liquor contained
9.4%; solids while the calcium oxide precipitanted,centrifuged liquor contained 9.1% solids.
Page 4
AMMONIA RECOVERY BY VACUUM DISTILLATIION The possibility of ammonia recovery by application of vacuum to the black liquor was investigated by the following experiment. A 300 ml. sample
of aronium sulfite black liquor (Cook 7) containing 26.2 grams per liter of ammonia was placedin a 2,000 ml. flask. The flask was connected through a Vacuum was
applied in such a manner that all the gas evacuated from the system passed through the boric acid trap.. After 90 minutes at a pressure of 25-30 mm. of mercury,
the trap was removed and titrated with standard hydrochloric acid as described for "Determination of Ammonia" in the Appendix. of ammonia. This tran contained only a trace
Heat was applied to the distilling flask and roughly half of the The titration of this Because of the inadequacy
of the equipment setup and the fact that up to this point only 0.08% of the ammonia in the liquor had been removed, this exporiment was abandoned.
containing 13.1
solids was placed in a distilling flask ANDconnected through a a boric acid trap. Approximately 450 ml. of the original 500 ml. titrated for ammonia. A fresh liquor raction acid
contained 2.5 grams or 19.1% of the ammonia in the liquor. was placed on the system, and
Distilling sweep
flask, a stream of nitrogen was introduced into the the vapors through the condenser.
dryness andthe boric acid trap again removed and titrated for fraction contained 0.04 r 0.3% of the total ammonia.
The solids in
whethor or
the flask proved impossible with the equipment used.. increments removed from range rather than at
the solids represents amonia removed over a temperature teh next boric acid trap titrated this trap contained
the range
a definite temperature.
A new boric acid trap was placed At this temperature The last
0.43 grams of ammonia were distilled out of the liquor solids. fraction was removed over the range of 2700 to 320 C. strong evolution of hydrogen sulfide occurred.
also distilled over which seemed to contain a considerable amount of ammionia. The total ammonia recovered front the liquor solids during this stage amounted
Fraction
gITH Recovered
1 2
2.49 o.04
0.3 5.0
1.2
3 4 5 6
0.65
0.16 0.43
0.87 4.64 grams
3.3
6.6
35.4 .
A 200 ml.
was placed in
a 2,000
to a gas diffusion disc through which the gas passed into the boric acid trap. Nitrogen was palled through the distilling flask in order to purge the system The first tran. was removed after grams
was placed on the system and 5.0 grams of purified calcium oxide added to the liquor in the flask. Distillation was again started and 57 ml. liwuor distilled
before the trap was removed. of the ori ginal. liquor distilled
A fresh boric acid trap was placed on the system and the to relative dryness. This increment contained 0.1 grams of
Another boric acid trap was placed on the system The flask was heated for
the condenser.
Localized
heating in the sand bath resulted in melting the bottom of the flask toward the end of the three hour heating period. as the
quantity
of ammonia recovered in this fraction may be lower than the The last boric acid trap contained 0.3 grams of ammonia or 6.85
true value.
of the total ammonia in the sample. Trap Numberr 1 2 3 4 Volume, ml. 106 57 29 37 Temperature, C. 100 100 100 100-290 ETH , grams 0.9 1.6 0.1 03 2.9 % of Total
3
23.4 42.1 1.8 6.8 74.1
DETERMINATION OF CHEMICAL BALANCE ON COOK 12 An effort was made on the cooks prior to Cook 12 to establish the distribution of chemicals after cooking. However, it was not possible on the
other cooks to account completely for the chemicals introduced into the cook.
Accordingly Cook 12 was made for the specific purpose of determining the distribution of the chemical. Every possible precaution was taken to insure that that all of the blow-down gases were
absorbed and that the loss of chemical by vaporization from the cooked chins
was kept to a.minimum. After the digester had been relieved to atmospheric
Page 8
Project 1516
Report 3
pressure and all liquor had been drained from the chips,
was replaced and the chips cooled almost to room temperature before durning. cooked, work.
drained chips were then weighed and a portion removed for experimental It was on this portion of cooked chips, the black liquor and the
absorbed relief gases that the complete nitrogen and sulfur balance was determined.
A weighed portion of the cooked chips were covered with distilled water and allowed to stand for 24 hours. The water was then drained and reIn all, the water was
placed with fresh water and soaked over the weekend. changed four times over a period of seven days.
with the British disintegrator and the water removed from the pulp in a Buchner funnel. The nitrogen and sulfur content were determined on the leach liquors and nitrogen only on the wood fiber. Sulfur was determined In all cases, nitrogen
and sulfur determinations were made according to the methods described in the Appendix. As showm in Tables I and II, the quantities of nitrogen and
sulfur in she leach liquor and chips were calculated back to the total cook weight. By so doing, the chemical balance for the entire cook was established.
pressure and all liquor had been drained from the chips, the cover of the digester was replaced and the chips cooled almost to room temperature before duing. The
cooked, drained chips were then weighed and a portion removed for experimental work. It was on this portion of cooked chins, the black liquor and the
absorbed relief gases that the complete nitrogen and sulfur balance was determined. A weighed portion of the cooked chips were covered with distilled water and allowed to stand for 24 hours. The water was then drained and re-
placed with fresh water and soaked over the weekend. changed four times over a period of seven days.
with the British disintergrator nd the water removed from the pulp in a Buclner funnel. The nitrogen and sulfur content were determined on the leach liquors Sulfur was determined In all cases, nitrogen
and sulfur determinations were made according to the methods described in the
Appendix. As shown in Tables I and II, the
sulfur in the leach liquor and chips were calculated back to the total cook weight. By so doing, the chemical balance for the entire cook was established.
TABLE I
NITROGEN BALANCE -- COOK 12
N2. grams
A) B) C) D) E) F) Black liquor through condenser Black liquor drained from chips Relief condensate Boric acid trap -- relief condensate Boric acid trap -Boric acid trap -black liquor relief [A above] top relief to zero p.s.i.
39.1 14.3
7.9 3.9
0.0 0.0 1.0 0.2
7.1
0.0 0.0 1.9 0.4
First leach liquor Second leach liquor Third leach liquor Fourth leach liquor Filtrate from chip defibering Pulp after defibering Totals
Data on leach liquors, filtrate and pulp are from small experiment, back to total cook.
TABLE II
SULFUR BALANCE -- COOK 12
Sulfur,
grams
Sulfur,
% of applied
A) Black liquor through condenser B) Black linuor drained from chips C) Relief condensate
G) Digester wash water
First leach liquor Second leach liquor Third leach liquor Fourth leach liquor Filtrate from chip defibering Pulp after defiberin- (Extract from soxilet extraction of airdry sample) Totels
4.7
136.0
Data on leach liquors, filtrate and pulp are from small experiment calculated back to total cook.
DISSCUSSION OF RESULTS
Of the several possible methods investigated for the recovery of ammonia front the black liquor, solution to the problem. only one showed promise of presenting a feasible
The methods of precipitating solids from the liquor likewise the attempted removal
did not appreciably reduce the solids content. of ammonia from the liquor by vacuum of the ammonia in the liquor.
solids by destructive distillation did not prove successful. equipment used was inadequate for this type of work.
charring of the solids resulted from the use of a sand bath for heating the distilling flask.
ammonia by the addition of calcium oxide to the liquor. of the ammonia present in distilled to dryness. the sample
The chemical balance on Cook 12 showed that about 30% of the nitrogen and sulfur were contained in the black liquor. Roughly 5 %of the nitrogen was
found in the relief gases while the remainder was present in the cooked chips. Recovery of both these chemicals from the pulp efficiency of the washing procedures. would depend entirely upon the washing should prove the wood would be the
more efficient then the laboratory method. defibered immediately after cooking , then
practice,
volume of liquor that could be evaporated would be the principle controlling factor. The recovery of sulfur either as sulfur dioxide or as elemental sulfur
APPENDIX
NITROGEN DETERMINATION
A) flask.
A 10 ml.
To this was added 10 ml. of concentrated sulfuric acid, 10-15 grams This was digested until then continued the quantities
of sodium sulfate and 0.5 grams of copper sulfate. the mixture in the flask an additional 15 minutes of sulfuric acid,
sodium sulfate and copper sulfate were increased proportionately After digestion was
the mixture was allowed to cool and solidify before continuing with The second stage consisted of distillation of The sample was diluted
the digested sample in the presence of caustic soda. with about 200 ml.
of distilled water and sufficient sodium hydroxide added to A Ejeldahl trap ws connected to the top of the This adapter
flask then through a water cooled condenser to an adapter tube. tube was lead into a flask containing 4% boric acid solution, being about an inch below at first the surface of the boric acid.
liquor had been distilled over, the boric acid trap was removed with 0.5 Nhydrochloric acid to a bromcresol green end point.
AMMONIA DETERMINATION
The determination of ammoniacal nitrogen in the black liquors was identical to the second stage of the method as described under "Nitrogen Determination."
SULFITE DETERMINATION
A sample of the liquor to be tested was pipetted into a beaker containing about 100 ml. of distilled water and sufficient ice to cool the mixture. About 10 ml. of acetic acid were added plus a few drops of starch The solution was then titrated with 0.1 X iodine solution.
indicator solution.
The titration for thiosulfate was the same as that described above except that 10 ml. of formalin was added to the solution before the titration. Ammonium sulfite calculations by this method take into account the difference in volume of iodine required to titrate the two solutions for the amount of ammonium sulfite present. TOTAL SOLIDS A 5 ml. liquor sample was pipetted into a tored, 70 mm. glass stopped weighing bottle. The bottle was then covered and weighed. A circulating oven
the oven overnight (16-17 hours) and, after cooling in the dessicator, weighed again to establish the ovendry weight. ASH A 5 ml. sample of the liquor was pipetted into a 45 x 45 mm. tored
Institute
The composition of sulfate black liquor tends to change on standing, Storage in.completely filled especially if access of air is permitted. and stoppered bottles serves to arrest such change; however, the tendency should be kept in mind and, in general, the analysis should be started and carried through without delay after sampling in order that results shall have maximum significance. Use recently boiled and cooled distilled water for all dilutions of liquor sample throughout the analysis. 1. Gravity
Determine the Baume gravity of the sample at 60 F., by means of a suitable hydrometer. Convert to specific gravity, if desired, from tables or by the formula: Sp. gr. = 145- Baume For maximum accuracy, a pyonometer. 2. Total Solids. determine the specific gravity at 20 C. by meanc o f
Pipet 10 ml. of the liquor into a tared platinum evaporating dish and weigh quickly to the nearest 5 ng. Divide the weight of liquor by the specific gravity, thus obtaining a check on the volume of liquor delivered. Place in an oven at 105 C. for 24 hours, cool in a desiccator, and weigh rapidly.
Note: If silica is to be determined, the use of platinum is essential. Otherwise porcelain may be employed. Ashing the alkaline mixture results in excessive attack on the porcelain, however, and generally speaking, the use of platinum dishes is highly preferable. 3. Sulfated Ash and Organic Matter.
Starting with a cold muffle furnace or a very low flame, heat the residue from the total solids determination until the organic matter is largely, but not completely, destroyed. Do not heat excessively. Cool, moisten the residue with a few ml. of water, add a drop of Methyl orange indicator solution and concentrated sulfuric acid, drop by drop, until there is an excess as shown by the bright pink color developed. Evaporate to fumes of SO, and thereafter heat at a moderate temperature until the excess
109-2
sulfuric acid has been removed Finnally, ignite un str qu all the organic matter is destroued but again avoid excessive heating. Cool in a desiecator and weigh. Assuring the residue ot be pure na,so4 calculate the sulfate ash to and report as per cent of the total
solids . report the difference between this value and 100 as the per
4.
Silica
Moisten the sulfated ash with 5 .. of concentrated HCl and , after a brief period. of contact, add 50 al. of hot water. Break up the residue with a stirring rod and bring the solution to boiling for a few minutes, making sure that the insoluble residue is completely disintegrated. Filter through a fine-grained, ashless filter paper into a 100-ml. volumetric flask, transferring the residue quantitatively to the filter by screening the sides ofthe dish with a rubber policoman and finally wiping our with a pice of quantitative filter paper which is then placed In the filter with the rest of the residue. Wash the residue on the filter with hot 1:20 HC1 and finally with water until the volumetric flask is filled to the mark. Transfer the filter paper bearing the residue to a platinum crucible, dry and smoke off the paper, and finally ignite strongly to constant weight at 900 . or more. Cool in a desiccat or and weigh quickly. Moisten the ignited residue with 1 ml. of water, add 4 or 5 drops of 1:2 H2 S0 4 and finally, with care, about 5 ml. of hydrofluoric acid. Evaporate off the hydrofluoric acid in a hood without boiling the liquid. When only sulfuric acid is left, increase the hat and fume it off, finally igniting strongly in the full flame of a Bunsen or Tirrill burner. Cool in a desiccator and weigh the loss in weight is the weight of SiO2 present.
5.
Total Sodium.
After filling to the mark and thorughly micing the contes of the volumetrick flash containing the filtrate and wash water from the silica dotermingation, remove a aliquot with an accurate pipet and proceed acc rding to Institute Method 104 (Gravimctric Determination of Sodium). Calculation:
6.
By means of a pipet transfer a 50-ml. aliquot of the accurately diluted filtrate from the silica determination to a 250-ml. beaker. Dilute to about 100 ml., add a few drops of Methyl red indicator solution and heat to boiling. Neutralize by dropwies addition of concentrated NH40H to the Methyl red end point (yellow) an, add a drop or two in excess. Filter through a quantitative filter paper and thoroughly wash the precipitate, quantitatively transferred to the filter, with hot water. Ignite strongly in a tared procelain crucible, cool, and weigh as A1203 + F 2 03 . Calculation: Weight of ignited oxides x 7. Sodium Sulfate. W
Pipet 25 ml . of the original liquor into a 250-cl. baker containing about 100 ml. of water and neutralize with HC1, adding 5 ml. of concentrated acid in excess. Filter and wash the precipitated organic materials throoughly with hot water, catching the filteato and washings in a 400-ml.. beaker. Boil gently for 10 minutes and cool. Just neutralize to Methyl orange by dropwise addition of concentrated NHIj,0H and then add 1 ml. of concentrated HC1. Dilute to about 250 ml. and, with a stirring rod in place to minimize the dancer of bumping heat to boiling. To the briskly soiling soluticn, add dropwise and with stirring 15 ml. of 10 per cent BaCl 2 solution. Maintain the solution near the boiling temperature floor 10 or 15 minutes end then set aside to settle and cool. The solution may be filtered with an hour with satisfactory results, although longer standin is preferable. Filter through a fine-grained, ashless filter paper, testing a small pertion of the clear filtrate with a drop of dilute HiiS0 4 to make sure that an excess of precipitant was present. Wash the precipitate on the filter with warn water until the wach water, acidified with HN03, gives no teat for chloride with Ar7N0 3. Remove the filter paper bearing the precipitate 5 to a weighed porcelain or platinun crucible and, after drying and smoking off the filter paper at lowr temperatures, Ignite to constant weight in an electric muffle furnace or over an ordinary burner. Cool and weigh. As a check against possible reduction of some of the BaSO4 in the ignition process, the ignited residue may be mosistend witha few drops of dilute H2 S04 and again heated, cooled, and weighed. Calculate the weight of BaS04 thus found to Na 2 S04 and express as grams per liter. Calculation: Grans of BaSO4 x 0.6086 x 40 = graus f Na 2 SO4 per liter.
8.
Total Sulfur.
Pipet 5 ml. of the liquor into a nickel crucible of about 50 ml. capacity, checking the volume delivered by rapid weighing to the nearest 5 ,g. and dividing by the specific gravity. Add cautiously, a little at a Uime, about 4 grams of Na2 02. Guard against mechanical loss through effervescence by keeping the crucible covered with a small watch glass while the reaction is actively progression. When all the sodium peroxide has been added , mix the contents of the crucible with a glass rod and finally rinse off the cover glass, the stirring rod, and the sides of the crucible into the bulk of the solution with a fine jet of water from a wash bottle, keeping the volume used for this purpose to a minimum. Evaporate to dryness and thereafter place the crucible in an electric muffle furnace or in a sand bath over small flame. Heat slowly to a temperature not exceeding dull red heat until the organic matter is destroyed and the mass is in clear and quiet fusion. If this condition is not achieved, add another portion of sodium peroxide. Do not heat excessively. Remove the crucible from the heat and rotate in an inclined position during cooling in order that tho volt is distributed over the sides and bottom of the crucible upon coolidification. After cooling, dissolve the molt in water and filter off any insoluble material, receiving the filtrate ald washings in a 400-al. beaker. Just neutralize the solution to Methyl orange with HC and add 1 ml. of concentrated acid in excess. If a turbidity of free sulfur is formed on acidification, or if the odor of H 2 S is at all evident, the determination must be discarded and another made employing a larger proportion of sodium peroxide. Dilute the solution to about 250-ml. and, with a stirring rod in place, boil gently for 5 minutes. Proceed further with the precipitation and estimation of the sulfate as BaS04 according to the procedure given for sodium sulfate, Section 7. Calculation: Grams of BaS0 4 x 0.1374 x 200 = grams of total S per liter. 9. Alkalinity.
conductometericTitration Apparatue. A suitable but inexpensive type of apparatus operating on ordinary 110-volt, 60-cycle lighting current has been described by McElhinney, Whittemore, and lynch (Paper Trade J., 106 no. 10, 37-41(March 10, 1938)). It consints of two 1/2-inch disk-shaped electrodes of bright platinum adustiably mounted in a vertical position, a 110-118 volt doorbell transforler, a coarse (500 ohm) and a fine (50 ohm) radio type rheostat, in series, for adjusting to constant voltage, a 30-milliampore a.c. ammeter, and a device for measuring the voltage across th, electrode. A 15-volt, 2000-ohm per volt, voltmeter or a unit consisting of a rectifier and a l-milliampere d.c. ammoter have been used for the purpose. A switch is used to close the circuit during readings and this may remain closed continuously during a titration. The proper poparation of the electrodes will depend on constructional features of the apparatus and the conductivity of the solution employed and must be adjusted to suit the case at hand. The adjustment, which may vary in the neighborhood of a half to one inch, must not change
Note: The size uf the samlle to be used for analysis varies with the type of liquor and concentration of the electrolytes present. It should be such that the voltage-current relationship obtained fall within a proper range relative to the instrument used. In this respect, the above procedure may require come modification as will beindicated by preliminary tril.
Alternative Method for Total Alkali. Pipet 10 ml. of the liquor into an iron or platinum dish. Evaporate to dryness and THEREAFTER ignite over a burner of perferably in an electric muffle furnace. Heat slowly at first, finally bringing the temperature to about 800 C. until the organic matter is decomposed . It is unnecessary to burn off all of the carbon resulting from breakdown of the organic compounds. After cooling, take up the residue with 50 ml. of hot water, breakin up the solid material as completly as possible with a stirring rod. Filter and wash the residue on the filter with another 50 ml. of hot water . Titrate the filtrate with standard 0.5 N HC1 using Methyl orange as the indicator. The volume of acid required represents an approximate value for either the total alkali or the total recoverable alkali, uncorrected for controversions duo to oxidation-reduction effects accompanying the incineration proccss and taking no cogniz inco of the sodium Silicate content. Calculation:
(uncorrected). dopending on the conditions of ignition, oxidation of sulfide and thiosulfate to sulfate or the reverse process may occur, thus introducing uncertainty as to the exact significance of the above determination To provide for this situation, proceed as follows: Boil the solution which has been neutralized to the Methyl orange end point for 5 minutes to expel H2 S, cool, add a little starch-indicator solution and titrate with standard 0.1 N iodine solution. The amount of iodine consuaic represents the thiosulfate content and the difference between this and the original thiosulfate content of the liquor is that formed or destroyed in the incineration process. Call this amount A. Calculation: Ml. of iodine solution x N x 0.158 x 100 - grans of Na 2 kS03s per liter (original) = A (grams of NnoS 2 0o formed per liter of liquor in the incineration process). Add 1 ml. of concentrated HC1 to the solution after the iodine titration, dilute to about 50 ml., haot to boiling and proceed with the determination of sulfate as described in Section 7. The difference between the sulfate content thus determined and that originally existing in the black liquor is that which has been formed or reduced in the incineration process. Call this amount B. Calculation:
Taking cognizance of the fact that A and B as defined by the above may be either positive or negative, correct the value for Total Alkali previously found by the following formula: Total alkali as grams of Na2 O per liter (uncorrected) + 0.437 B + 0.392 A = (corrected). Total alkali as grams of Na20 per liter As calculated, the corrected value for Total Alkali includes neither the thiosulfate nor sulfate contents. A figure representing the Total Recoverable Alkali may be derived from either the corrected or uncorrctAd value for Total Alkali by add ng respectively the thiosulfate and sulfate contents (calculated to Na20) of the original liquor as separately determined or the thiosulfate and sulfate contents as determined after incineration. The result thus obtained for the Tot:l Recovera ble Alkali as well as the corrected value for the total alkali includes the sodium sulfite and sodium silicate contents. B. Active Alkali (Na2 0 as NaOH and Na2 S)
Pipet 100 ml. of liquor into a 500-ml. volumetric flask partially filled with C02 -frec water. Add 100 ml. of 10 per cent BaC12 solution, dilute. to the mark, mix thoroughly and sot aside to allow the precipitate to settle. Tost a small portion of the supernatant liquid for .excess precipitant by adding a drop of dilute sulfuric acid. If no excess is present, repeat the preparation using a larger quantity of BaC1 2 . Remove a 100-ml. portion of the supernatant solution and titrate potentiometrically, employing a glass electrode, with 0.5 N HC1 until a pH of 4 or lower has been reached. Prepare a titration graph by plotting pH values as ordinates against volume of standard acid added. Note the volume of acid tequired to reach a pH of 8.3, corresponding to
the phcnolphthalein end point and reporesentingthe neutralization of all
the NaOH snd conversion of sulfide to bisulfide. From this value together with that for the Na2 S content, as determined according to the following section, calculate and report the Active Alkali as grams of Na20 per liter. A value for tho NaOH content of the liquor may be found by difference. Calculations: (Ml. of acid x N x 0.031 x 50) + (0.397 x grams of Na2 S per liter) =
Active Alkali as grams of Na 2 0 per liter.
(M1. Note:
of acirl x N-x 0.040 x 50) - (0.515 x grams of Na 2 S p-r liter) = grams of N30H per liter.
The values for the active alkali and th; NaOH contents thus determined include strongly hydrolyzed sodium-organic compounds present in the supcrnatant liquor and therefore are not exact as represented.
By means of a pipet, remove a 50-ml. portion of the supernatant solution prepared for the active alkali determination and transfer to a 150-ml. distilling flask equipped with a dropping funnel and connected on one side through a wash bottle containing water to a tank of carbon dioxide or nitrogen and on the other, through the delivery arm and a condenser, to two wash bottles containing an accurately measured volume of standard 0.1 N iodine solution. There should be a substantial excess of iodine, the total volume used being at least 10 ml. more than that subsequently consumed in the reaction with the .evolvod H2 S, and the majority should be placed in the first trap. A third wash bottle containing about 2 ml. accuratelyy measured) of standard 0.1 N thiosulfate solution serves to retain any iodine that might escape otherwise. The reagents in all three traps may be diluted with water to afford an adequate depth of solution for officient absorption. Measure into the. dropping funnel by means of a burct or Mohr pipet such a volume of standard normal acid (HO1 or H2SO0) as will neutralize the sample to a pH of 4. The required amount may be derivoed from the potontiometic titration carried out in Section 9. With the apparatus and materials completely assembled, swaesp out the system with r moderate passage of gas for a few minutes (the gas inlet tube, with a constricted orifice, should extend below the surface of the solution). Temporalily discontinue the gas passage and lot the acid run into the sample, rinsing the funnel into the flask with about 20 m. . of water and taking care that no evolved gas escapes through the dropping funnel. With the stopcock on the dropping funnel closed, resume the passage of inert gas at about 2 small bubbles per second and bring a becker or boiling water into position submerging the bulb of the distillation flask. Continue to heat in the boiling water bath for 30 minutes. Disconnect the flask from the condenser, rinse down the latter with a few ml.. of water and combine the contents of the three wash bottles titrate the excess iodine with standard 0.1 N thisulfate solution. The total volume of thiosulfate involved in reaction with the excess iodine includes that originally placed in the third. wash bottle as well as that required in the final titration. caluculation the iodine consumer to gra of Na2 S per liter of original liquor. Calculation:
11.
Pipet 50 m.. of the liquor into a 500-m1. volumetric flask, add 25 ml. of glycerol, and precipitate the sulfide and, incidentally, most of the organic matter by the addition of an excess of a suspension of ZnCO 3 . The latter may be prepared by adding at room temperature and with constant stirring 150 rml. of 10 per cent Ia2 CO 3 solution to a solution of 30 g. of ZnS04.7 H20. After addition of the ZnCO 3 suspension to the liquor sample in the volumetric flask, the nixture is diluted to the mark,
Institute Tentitve
Method 109-9
miced thoroughly, and filtered through a Buchner funnel using suction. Test for complete precipitation of sulfide. Cool the filtrate in an ice bath or refrigerator and pipot 100 ml. into a 500 ml. erlenmeyer flask containing 100 g. of ice. Add a few ml. of starch-indicator solution and sufficient acetic acid (predctermined by a rough test on a small portion separately removed) to acidify the solution. Quickly cover the neck of the flask. with a rubber diaphragm (e.g., a piece of dental dam)and secure it in position with a rubber band. (This precaution is especially necessary if large amounts of sulfite are present.) Puncture the rubber diaphragm with a noodle, insert the tip of a buret containing standard 0.1 N iodine solution through the aperture thus provided, and titrate until the blue color produced on additnon of 1 drop of iodine solution persists for 10 or 15 seconds. Call this titration A. To a second 100 ml. portion of the filtrate, also in the presence of ice, add 10 m.. of formalin and swirl to mic . add starch and the same amount of acetic acid as used in the first titration and titrate with standard iodine solution until an end point of corresponding duration is reached. Call this titration B. Calculations:
Note: In general, the value thus determined for the thiosufate by this mathed will be some what high due to interforece from organic reducin materil remaining in the supernot solution.
AMMONIUM SULFITE PULPING OF WHITE BIRCH INTRODUCTION Consolidated Water Power and Paper Co. intermittently has trouble with pitch removal when pulping white birch. In investigating this problem,
several experimental cooks were made on white birch chips, utilizing ammonium sulfite or sodium base sulfite as the pulping agent. The present report
covers the procedures used in making these cooks and the results of tests made on the produced pulps. RAW MATERIALS Bolts of white birch were taken from wood storage for use in the following experiments. This wood was received at the Institute on July 26, Since that time
1950. from Oxford Paper Company for use in Project 15 3 4. the wood has been kept in uncovered storage.
The liquor used in making the experimental cooks was prepared from c.p. chemicals. EXPERIMENTAL PROCEDURE AND RESULTS The white birch bolts were chipped in the 36-inch Carthage laboratory chipper, set to deliver nominal 3/4-inch chips. The chips were screened, hand-
sorted, and divided into digester charges according to the method outlined in
FORM 73
the chips into individual charges showed 20.07% moisture in the chips.
it became evident that additional chips would be required, a second lot of wood was chipped and digester charges were prepared as above. This second lot
first lot; the remaining cooks were made from the secondlot. All pulping experiments were carried out in stationary, vertical digester No. 4. The capacity and characteristics of this digester are outlined in Pulping Group Procedure No. 40. The cooking liquor used in making the first cook (Cook 17) was prepared by dissolving ammonium sulfite crystals in water and adding sufficient ammonium hydroxide to achieve the desired ammonia concentration in the liquor, Liquor analysis was made according to the Palmrose method for total sulfite and it was assumed that the added ammonium hydroxide was 28% ammonia by weight. A water ratio of 6.0 ml./g. of ovendry wood was used and 15% ammonia
and 20% sulfur dioxide (based on the ovendry weight of wood) were applied. These same ratios were used in subsequent cooks unless otherwise noted. Cooking was carried out at a maximum digester pressure of 80 p.s.i., using 3 hours of the 16 total hours' cooking time to arrive at this pressure. maximum temperature found during the cook was 157C. The
were encountered during the cook and temperature and pressure could not be maintained during the final 0.5 hour of cooking. p.S.i. The cook was blown at 70
Cooking conditions are summarized in Table I. Only a small amount of the total charge of cooked chips was blown
Project 1516
Report 4 June 24, 1952 Page 3
The remainder were washed from the digester through the The chips were quite hard and were not A small portion of the
cooked chips was disintegrated in the 8-inch laboratory Bauer and then screened
The permanganate
number of the screened pulp was found to be 332 (determined according to Institute Method 410 4 0-cc,
basis).
It was felt that the bad liquor leaks encountered in the previous cook were partially responsible for the lack of pulping found. The cook was In this
cook (Cook 18) the liquor was prepared by bubbling sulfur dioxide gas through ammonium hydroxide. The S02 content of the liquor was determined according to the Palmrose method, and the ammonia content was determined by the Kjeldahl method. to 1E 3 No attempt was made to adjust the liquor to the desired ratio of S02 The amount of IE3 required to achieve this ratio was added as ammonium
hydroxide, Only a very slight liquor leak was encountered during this cook, After approximately 8-1/4 hours of cooking the pressure gage indicated rapid loss of pressure in the digester. The temperature remained constant, however,
and checks showed that the top relief line, including the line to the pressure gage, had become plugged. Upon disassembly of this line, it was found that This same
ammonium sulfite had crystallized, completely blocking the line. trouble was encountered in several subsequent cooks.
at the temperature being maintained at the time the line became blocked.
only a very small portion of the chips were removed from the digester.
remaining chips were washed from the digester using a jet of hot water.
As
in the previous cook, the chips were very hard and had to be disintegrated by passing them through the 8-inch Bauer. Only sufficient pulp was de-
fibered and screened to determine the permanganate number and the percentage of ether extractables. This latter test was carried out according to InstiThe results of the above
tests are shown in Table I together with the cooking conditions used. The conditions used in making the next two cooks (Cooks 19 and 20) duplicated those used in Cook 18 except for the cooking schedule. Because
of the difficulty encountered with the previous cooks in washing the raw cooked chips from the digester, a stainless steel basket was used for subsequent cooks. fit The chips were charged to the digester in the basket, which At the end of the cook
the digester was relieved to atmospheric pressure, the cover removed, and the basket containing the cooked chips was lifted out. The chips were dumped into
a blowpit for washing according to the standard procedure. In Cook 19 the cooking schedule for the first 12 hours was the same as that previously used. At this point the digester was relieved through a
top relief line, maintaining 80 p.s.i. pressure by increasing the temperature. While relieving, liquor samples for pH determination were removed periodically through a watercooled condenser. pH dropped to 8.1. Top relief was discontinued when the liquor
The pH continued to drop after top relief had been dieA gradual rise from this point to the
Project 1516
Report 4 June 24, 1952 Page
TABLE I
SUMMARY OF COOKING CONDITIONS AND PRODUCT VARIABLES (Cooks 17 - 21) Raw Material: White Birch
Cook No. Applied chemical Water ratio (OD), Cooking Schedule: Max. pressure, p. si. Time to max., Time at max., hr. hr. SO, Imj* cc./g. % %
17 20 15 5.1
18 20 15 6.0
19
20
20
21
15
20 15
30*
16
6.0
6.0
6.0
80 3 13
80 3 13
80
80 3
13 149 4
80 3
3
13 149
12
13 160 3
157
160 C Time of incrase ot Product Variables: Black liquor pH Permanganate number Unscreened yield, % Screened yield, % Ether extractables, % hr.
8,1
6.4
15.9
27.9
65.4
65.3 58.4 1.82
0.28
0.31
0.60
end of the cook gave a final liquor of pH 7.6. As previously stated, the digester pressure was maintained constant at 80 p.s.i. during the top relief by increasing the temperature. When
equilibrium was reached after top relief was stopped, the digester temperature was found to be 160C. This condition was maintained until the end of the cook
The cooked chips produced in Cook 19 were hard and again it was necessary to defiber them in the 8-inch Bauer. and screened in order to determine yield. The entire cook was Bauered
of tests made on the screened pulp are shown in Table I. Cook 20 was a duplicate of Cook 19 except that the top relief and consequently temperature increase was carried out after four hours of cooking time or after one hour at maximum pressure. As in the previous cook, the pH
of the liquor continued to drop after top relief was discontinued, reaching a minimum value of 7.2. of 8.1. A gradual rise from this point gave a final liquor pH The
defibered pulp was screened and tested as before, and the results are shown in Table I. In order to obtain better pulping, Cook 21 was made using the neutral ammonium sulfite salt as the active chemical and raising the applied chemical to 30% sulfur dioxide (based on the ovendry wood). of neutral salt required to give Theoretically the amount A
maximum temperature of 160C. was attained in three hours and some top relief was required in order not to exceed the maximum pressure of 80 p.s.i. The pH
of the neutral salt, at the concentration used in the digester, was found to
Project 1516
Report 4
be 8.0.
During the early part of the cook, the pH dropped quite rapidly, reachFrom this point the drop in pH was not
was maintained throughout the remainder of the cook. The pulp obtained from this cook was much softer than any of the previous pulps and it defibered quite readily during the washing operation. The washed pulp was screened, without further mechanical defibering. mately 10-15% of the pulp was rejected by the screen. Approxi-
fibered in the 8-inch Bauer and rescreened, the through-fraction being combined with the screened pulp obtained from the original screening operation. The
rejected portion from the second screening represented less than 0.04% of the pulp produced. Results of tests made on this pulp are shown in Table I.
This last cook (Cook 21) was made almost entirely on the acid side, and test showed that more pitch was present in the pulp produced in this cook than in the rawer pulps produced in the previous cooke. It appeared that it
was necessary to cook on the acid side in order to produce a satisfactory pulp and still remain on the alkaline side in order to remove the pitch. ation of these two conditions was attempted in Cook 22. The chip charge was split in half (airdry basis). One-half was A combin-
charged to the digester in the normal manner and the second half was charged in a specially constructed stainless steel wire cloth basket. The basket con-
taining the chips was placed on top of the chips already in the digester. The first phase of this cook was a normal soda-base sulfite cook using a liquor ratio of 6.0:1. Liquor analysis showed 7.18% total, 6.17% free, and
Report 4
1.01% combined SO2 . A maximum temperature of 148C. and a maximum pressure of 80 p.si. were used. Total cooking time was 8 hours, using 3 hours to reach
110 0 C., 3 hours from 110 to maximum temperature and 2 hours at maximum temperature. Final relief to atmospheric pressure was extended over the last 1.25hours of cooking time. hem the digester was relieved to atmospheric pressure the cover was removed and the basket containing the top half of the chip charge was lifted out. These chipsere dumped into a blowpit and washed according to the standard
procedure. All liquor was drained from the chips remaining in the digester. was accomplished through the liquor line, leaving the blow valve intact. After the liquor was drained, the drain valve was closed and 9 liters of hot water was poured over the chips. This amount of water gave good chip coverage. This
With the pump circulating this water through the chips, 100 ml. of concentrated sodium hydroxide solution was added. This amount of sodium hydroxide represented The liquor was circulated over The cover
the chips for two minutes and the liquor pH at this point was 9.1.
was replaced and temperature and pressure increased to 160C. and 80 p.s.i. in 15 minutes. These conditions were maintained for 60 minutes. The cook was
blown at 35 p.s.i. digester pressure, reaching this pressure by normal cooling in 10 minutes after the steam was turned off. Unfortunately the amount of
caustic added proved insufficient to maintain alkaline conditions in the digester throughout this phase of the cook. The final liquor pH was found to be 4.7.
The two pulps produced in this cook were screened and tested Separately in the manner previously described. The results are shown in Table II.
Project 1516
Report 4
June 24, 1952 Page 8
TABLE II SUMMARY OF COOKING CONDITIONS AND PRODUCT VARIABLES (Cooks 22 & 23) Raw Materials White Birch
Cook
22-1
22-2* ---
23
Liquor analysis:
Total SO2,
Free SO2 % Combine S02, %
7.18
6.17 1.01 6.0
6.55
530 1.25 6.0
3.0
7.0
tempo, hr.
3.0
0.25
5.0
2.0
8.0 14
80
1.0
1.25 160
80
4.0
16.0 132
80
Product Variables: Permanganate number Unscreened yield, % 9.0 49.2 6.7 46.9 8.6 49.8
Screened yield, %
Ether extractables. %
49.1
0.73
46.7
0.72
49.8
1.06
Project 1516
Report 4 June 24, 1952 Page 9 The final cook carried out under this program to date was a soda-base sulfite cook using a long-cooking scheduled A liquor ratio of 6.0 cc./g. of
ovendry wood was used and the liquor analysis showed 6.55% total, 5.30% free, and 1.25% combined SO2 . The cooking schedule is shown in Table II.
DISCUSSIOI None of the cooks described in this report was successful in both pulping and pitch removal. In some cases good pitch removal was obtained, but Where good pulps
the conditions employed were too mild to produce a good pulp. were produced, pitch removal was inadequate.
The conditions employed in Cook 22 seem to hold the most promise. With the proper setup to insure alkaline conditions throughout the second phase of the cook, better pitch removal might be obtained. At the same time, how-
rsh/jh
MEMORANDUM
From D. J. MacL To The Files
Date
About a year ago it was decided that a thorough review of the literature should be made with respect to all aspects of ammonia and ammonia compounds as pulping agents. It was further decieed that this review should lead to two reports--the first report classifying the relevant literature on a subject basis, and a second report reviewing the literature critically-for the purpose of pointing up the inadequacies in our knowledge and understanding of ammonia and ammonia compounds as pulping agents, and thus outlining areas for future investigation and research in this field. Don Helleur of the Pulping Group was assigned this literature work. In August, 1953, the first report was completed and subsequently published (TAPPI 37, no. l:177A-182A(Jan., 1954)). That paper is included in this project file as Project Report 4 A report dealing with the second phase of the literature survey was completed about the end of 1953, and is included in the file of this project as Project Report 3.6
djm/jh
FORM 73
The first
patent was issued to Braun in 1902 (34, 69, 100). In recent years, not only has it been receiving increasing attention and interest but it has also been used fairly extensively to produce commercial tonnages of pulp. The major part of this use and interest has centered around the ammonium bisulphite process. To aid those who are interested in the literature of this particular field, references have been collected and classified for the period 1900 to June, 1953. In classifying these references, an attempt has been made to anticipate the interests of both the operational and technical approaches to the subject. No attempt has been made to review the material critically. Reference numbers below 100 are for technical papers and those above 100 are for patents.
APPLICATION TO SPECIFIC FIBROUS Woods MATERIALS
Some of these studies were directed to certain wood species generally considered difficult to pulp with calcium bisulphite liquors. For example, in the case of Douglas-fir, chips were pretreated with ammonium hydroxide to extract resinous materials, then ammonium bisulphite liquor was added to cook the wood (10). Studies on Douglas-fir without pretreatment include (11), (18), and (58). Specific wood species used to study the process variables include: white fir (36); aspen, in attempt to yield a purified pulp for chemical conversion (70); longleaf pine, using an extraction with liquid sulphur dioxide followed by the ammonium bisulphite process (57); pine and beech (65); mixed hardwoods (birch, maple, beech) using the ammonia neutral sulphite and the bisulphite processes, with base comparisons (77); Bordeaux pine (15).
Agricultural Residues
Konig Process. Wood is heated with ammonium hydroxide and this treatment is followed by treatment with a mineral acid (or vice versa ) (101); a further patent with the emphasis on by-product recovery was (102). Disadvantages of this process are discussed in (31) and general comments given in (30, 31). Gluteor. The principle of the process lies in the saponification of casein to obtain a product which under certain conditions of pressure and temperature evolves nascent ammonia which can be used for cooking fibrous materials. Merits and demerits are discussed in (8, 29). Billwiller. A broad patented process making use of such cooking chemicals as ammonia, sodium carbonate, hydrogen sulphide, etc., with the emphasis on the use of catalysts and of a pretreatment using these chemicals followed by known cooking processes (i.e., prior to 1919) (108). For the use of ammonium hydroxide specifically, see (111). Discussion of: merits (12) and general process (6). Other Processes. Pulping agricultural residues (119). See also (II, IV, V, VI) under miscellaneous cooking processes. Pretreatments with ammonium hydroxide (116) plus preferably some ammonium sulphite (120) to remove resinous materials (118) followed by the ammonium bisulphite process (10, 121, 140); or followed by sulphuric acid (50). See also (X) under miscellaneous
Ammonium Sulphite (Neutral and Alkaline)
The first patent by Braun (100) described a more or less neutral sulphite pulping process. Comments on this process (25). Another patent is (105). A later patent tended to the more alkaline side (34, 104). One tending to the acid is (106). Pulping of straw and wood (15). Reviews covering this type (as well as those in the acid range) are (34,68,73). Its use in semichemical pulping (48). See also (I, III, IV, VI) under miscellaneous.
Ammonium Bisulphite (Excess Sulphurous Acid)
Short study using ammonium sulphite neutral process on straw (15); bisulphite on straw (7) with base comparisons; use of ammonium hydroxide on various
materials (corn, oats, and straw stalks) (8, 62, 102, 119).
D. E HELLEUR, Technical Associate, Appleton, Wis The Institute of Paper Chemistry,
Cross (and Englestad) Process. Using low combined sulphur dioxide (0.5 to 0.25%) (109, 110); laboratory studies on this process are (22), and general reports (28, 76); references made to it in the studies of Dorec and Hall (26, 27). Others are (106, 112, 117, 118, 121, 122, 125, 129,
177 A
T A P IP
January 1954
131, 134, 140,141, 142, 143, and 146). See also (I, IV, VI, IX, X, XIII) under miscellaneous Using a liquid sulphur dioxide pretreatment (on longleaf pine) followed by the bisulphite (57). Comments on this study (65); others (7, 10, 11, 20, 35, 38). General reviews covering the process are (17, 34, 38, 85).
Miscellaneous Cooking Processes
bases including ammonia (63); an industrial review of the sulphite (acid) process including evaporation of liquors (ammonium included) (79); comparison of the various sulphite pulping methods from the point of view of the spent liquors (71).
Evaporation
Under pressure to recover chemicals (130, 133). allied subject is concentration by recycling (144).
Evaporating and Burning (Recovery of Heat)
An
(I) Gaseous Cooking. Sammet and Merrill treat fibrous materials with gaseous ammonia and sulphur dioxide and steam (103); a gaseous pretreatment laboratory trial (16). (II) Using ammonia and steam only, there are (76, 139). (III) A somewhat novel way of arriving at an ammonium sulphite cooking liquor is to treat a calcium bisulphite solution with ammonia, thus forming an ammonium sulphite solution with the precipitation of calcium sulphite. The fibrous material is then cooked with this ammonium sulphite liquor (104). (IV) A very broad patent covering a wide pH range, and using such chemicals as ammonia, sulphur dioxide, steam (separately or together) is (107) (V) On processes using a solution of cyanide or cyanate which forms ammonia by saponification with water; supposedly, the difficulties in the decomposition of wood by ammnoium hydroxide are thereby avoided (115). (VI) Another very broad patent covers pulping with ammonia and sulphur dioxide as well as the sulphite, sulphate, carbonate, and sulphide salts of ammonium either separately or in combination; for certain wood the ammonium bisulphite is preferred; for materials like cotton linters, amnona; agricultural residues, slightly alkaline amonumn sulphite; a "kraft" cook also can be used, e.g, 2% ammonia and 2% ammonium sulphide; etc (123). (VII) To avoid the high cost ot ammonia, Richter advocates cooking with 1 to 8% ammonium sulphate and 3 to 8% free sulphur dioxide (117). (VIII) Processes cooking with mixtures of other bases (e.g., NaOH, Na 2S, Na acetate, etc.) together
with ammonia are (124, 126)
Included with a cooking process in heat recovery step (144, 146); commercial trials are reported (14, 33, 46, 61, 81).
Recovery of Cooking Chemicals
Ammonia. Distillation with a base (127, 128, 132, 133), with lime as the base (127, 128), with kraft black liquor (21, 132), with magnesium oxide as the base (146), by pyrolysis (53, 71, 137), by ion exchange (deashing) (52), by steam stripping (52), and by vacuum evaporation (52). Sulphur Dioxide. Commercial trials, sulphur dioxide liberated during the burning step (14,61,81); recovered during evaporation (130, 133). Ammonia and Sulphur Dioxide. Processes claiming to recover both: Solvay process (71, 133); by boiling under pressure at approximate 40% concentration (137); by boiling to liberate sulphur dioxide, then addition of a base to liberate ammonia (133); by a process of pyrolysis on the concentrated solution or the dry solids (138); pertinent to this latter process is (53); treating with magnesia to liberate ammonia and to convert liquor to magnesium base, evaporating and burning the converted liquor to yield magnesia for reuse and sulphur dioxide, which is recovered from the combustion gases using the liberated ammonia (146).
Other Liquor Utilization
(IX) To cook with a high percentage of sulphur dioxide (5 to 26%) an aqueous solution of ethyl alcohol was employed, to which was also added 0.7% ammonia (60). (X) Another process pretreats with excess liquid ammonia, the excess being removed to be followed by a solution of sulphurous acid, such that in effect the final cooking is done by the usual bisulphite process (131). (XI) Another suggests cooking with ammonium sulphate with the addition of organic nitrogen compounds-e g , aniline, trethanolamine, etc. (135). (XII) Another m the same vein suggests using ammonium hydroxide together with mixtures of soaps, oils, fats, alkalies, sodium sibcate, potassium chloride,
etc. (136).
Fertilizers-(5,55). A general discussion of producing ammonia for fertilizers from wood waste is (66); liquor neutralized with basic calcium phosphate rock, etc.. evaporated and dried (114); as an organic cation exchanger (145); stabilizer in bituminous emulsions (143); re-using the spent liquor in cooking operations after fortification with cooking chemicals (144); fermentation to ethanol (1). Miscellaneous uses of the spent liquor are adhesives, wetting agents, dispersants, soil conditioner, yeast nutrient, etc. One such product is sold under the trademark Orzan (23, 55). A process purports to produce decomposition products by neutralizing the liquor with ammonia, and heating with carbon to yield acetic, formic, and oxalic acids and activated carbon (113).
MILLS AND OPERATIONS
(XIII) A process re-using spent liquors after fortification with cooking chemicals is (144)
SPENT LIQUORS-UTIIIZATION Recovery in General
Literature references to mills that are using or have used ammonium-base processes either on full-scale operations or as short mill trials are listed below. Except for one in Norway, the mills listed are in the United States:
1. 2. American Box Board Co, Filer City, Mich. (48). Consolidated Water Power &Paper Co, Wisconsin Rapids, Wis., and Interlake Dv , Appleton, Wis (2, 46, 48). Vol. 37, No. I January 1954 T AP P I
4. 5. 6. 7. 8. 9.
Crown Zellerbach Corp., Lebanon mill (also pilot plant study of evaporation and burning the spent liquor) (14, 51, 61, 81). Diamond Match Co, Ogdensburgmill (37). Eastern Corp., Lincoln and South Brewer mills (51). International Paper Co., Southern Kraft Div. (48). Rayonier, Inc., Shelton, Wash (3, 5, 33, 51, 65). Toten Cellulosefabrik, Nygard (Norway) (24, 35, 51, 75). Wausau Paper Mills Co., Brokaw, Wis. (2, 82).
2 3. 4.
Organization and implementation of an ammoniabase trial discussed (34) Design of ammonia-base sulphite acid systems (42, 43, 44,45,54,82,83). Preparation of raw cooking acid (13) Digester linings (78). Corrosion of linings (40). Review of the field and a report of the progress (48, 49, 65, 72, 75).
ANALYSIS, TESTING, AND GEN Eral CIIEMISTIRY
5. 6.
7.
Testing of the cooking liquor with a modified Palmrose method (13). Conductometric analysis of the pulping liquors for such as ammonium hydroxide, carbonate, sulphite, bisulphite, and acetate (84). Sulphite process (22, 26, 27, 32, 36, 56, 58). Chemistry of reactions, cooking variables, etc., kinetics of, penetration studies (16, 19, 36, 39); ammonia pretreatment (16, 59); system: ammonia, sulphur dioxide, and water (42, 43, 44, 45); cooking liquor (56); spent liquor (27, 32).
ADVANTAGES CLAIMED FOR AMMONIA-BASE PULPING
8. 9 10
11.
12. 13
Claims and comparisons together with their references are listed below. Many of these claims, it will be noted, are not specific to ammonia-base but exist only when taken in comparison with some other base. Practically all the claims are made with respect to the ammonium bisulphite process. 1. Ease of raw material handling (i.e., cooking chemicals) (4, 37). 2. Amenable to the pulping of difficult woods (9, 10, 11, 18, 58). 3. Superior quality of raw acid (4, 37, 54). 4. Superior condition of the digester equipment (4). 5. Cooking variables (4, 58, 77); superior penetration (9, 19, 74, 81); lower cooking temperatures (24, 35, 67, 72, 81); reduced cooking time (28, 37, 67).
14. 15.
1i
17
18
7.
8. Lower bleach requirements (4) 9. Plant maintenance less (51, 81). 10. Recovery of heat and chemicals (14, 24, 35); and all of section "Spent Liquors-Utilization."
General reviews (mainly bibliographic in nature) have been incorporated in the above For ready reference, they are (34, 37, 68, 75, 79, 85)
LITERATURE CITED References to the Bulletin (Libary Notes) of The Institute of Paper Chemistry (B.I.P.C.) and Chemical Abstracts (C A ) are included in all cases where the abstract gives a summary of the article in question. 1. Agar, Hilda, P., and McCarthy, Joseph, Sulphite waste liquor. I. Fermentation of ethanol of cone. Ca. Mg, and January 1954 Vol. 37, No. I
23. 24 25. 26
NI sulphite waste liquor. Tappi 34, No 3: 126-131 (March, 1951); B I P.C. 21: 584, C A. 45: 4447. Ammonia in more mills; liquor burning at Badger and [ntellake Pulp & Paper 25, No. 3: 64 (March, 1951); RI.P.C. 21: 585. Ammonia pulping report. Paper Ind. 33, No. 12: 14381439 (March, 1952); B.I.P.C. 22: 614. Aries, Robert S., Recent developments in the utilization of sulphite waste liquors. Northeastern Wood Utilization Council Bull. No. 14- 97-121 (Jan, 1947), B.I.P.C. 17: 380. Aries, Robert S., Research on lignin as a soil builder Northeastern Wood Utilization Council Bull. No. 7: 56-62 (Oct. 1945'; C.A 40: 1623; B I.P.C. 16: 183. Arnot. J. Melrose, Some new processes for the separation of fibrous cellulose from plant substances. World's Paper Trade Rev. 95, No 11: 961-962, 964 (March 13, 1931); B.I.P.C. 1, No. 9: 20. Aronovsky, S. I, Ernst, A J.. Sutcliffe, H. M, and Nelson, G H. Agricultural residue pulps-comparison of pulping processes Tech. Assoc Papers 31: 299-304 (June, 1948); Paper Trade J. 126, No 26: 78-83 (June 24, 1948), C.A. 42 5662; B A. 1948B. IT: 387; B.I P C 18: 790. Barbier, Emile, Imitation kraft paper from straw by means of the so-called Gluteor process. Papetcie 49, No 12: 538-543 (June.25, 1927); T.S. 86: 7; C.A. 21:2984. Benson, Henry, K, Ammonia pulping of wood. Pulp & Paper24, No. 8:74, 76 (July, 1950), B I P.C. 20: 907. Benson, H. K., Erwin, R. P, Hendrcklson, .1. R., and Tershin, J. A., The pulping of Douglas-fir by ammonia-base liquor. Paper Trade. . 99. No. 12: 87-89 (Sept. 20, 1934); Tech. Assoc Papers, 18: 513-515; discussion, 486-487 (June, 1935): C.A 28 7522; 7.S 99: 322; B.I.P.C. 5: 46. Benson, H. K., and Lucas, J. E , The pulping of Douglasfir with ammonium bisulphite. Paper rade . 111, No. 7:32-34 (Aug. 15, 1940); C.A 34:8265; B.C.P.A 1940B: 786; BI.P.C. 11:35. Billwiller cooking process. Zellstoff Pape 11, No. 4: 197 (April, 1931); T.S. 94: 3. Bishop, F. F., and Honstead, J. F, Ammonia-base sulphite pulping liquors-their preparation and analysis. Tappi 34, No. 7:318-323 (July, 1951); C.A. 46:255; B.A. 1951B, II: 1009: B I.P.C. 21:877. Booth, Kenneth, G , Ammonia sulphite process. Pulp & Paper 26, No. 9: 80, 82, 84 (Aug, 1952); B.I.P.C 23: 754. Brot, M V., and Hirschel, M., Treatment of straw and of woods ith sodium sulphite and ammonium sulphite. Papier 29, No 1 75-80 (Jan , 1926); Paper Ind. 8, No. 1:97, 99, 101 (April, 1926); '.S 83: 100; C.A. 20 1322. Bryde, O., The significance of penetration in the sulphite cook, the possibility for improving penetration by artificial means. Norsk Skogind. 3, No 7: 169-172 (July, 1949); B.I P C. 20: 192 Cable, Donald, E, Sulphite pulp from spruce. Paper Trade .. 85, No. 13: 43-49; No. 14: 58-63; No. 15: 50-55 (Sept, 29, Oct. 6, 13, 1927); Pulp Paper Mag Canada 25, No. 39: 1215-1222; No 41: 1299-1305, No. 42: 13311332; No 44: 1405-1408, 1422, 1424 (Sept. 29, Oct 13, 20, Nov 3, 1927); Zellstoff u. Paper 8, No 6: 372-373 (June, 1928); T.S.87:28; CA 22: 1681. Chidester. G. H, and McGovern, J N., Sulphite pulp from Douglas-fir. Paper Tiade J. 113, No. 9: 34-38 (Aug. 28, 1941); Tech Assoc. Papers 24: 226-230 (June. 1941); Paper lnd 28, No. 3. 288 (June, 1941); B I.P.C 12: 57. Christensen, G N, and Williams, E . , Diffusion in Wood [II. Ion selection and its effect on the diffusion ol electrolytes. Australian J. Applied Sri. 2: 440-453 (1951) Colter, John, S., Use of recovered ammona in sulpite pulping Paper Trade.. 136, No 2: 13 (June 5, 1953) Cooper, Stuart, R. Ammonia recovery from sulphte waste liquor. Paper Trade J. 136, No 23: 13 (June 5, 1953). Cross, C. F, and Engelstad, A, The action of aqueous sulphurous acid on hgnocellulose. II. . Soc. Chem. Ind 44, No. 23: 267-270 (June 5, 1925); Paper Trade .1 81. No. 8:45-48 (Aug 20, 1925), T.S. 82: 8; C A 19 2742. Crown Zellerbach corp. Add waste utilization. Chem. Weck 70, No 15 4 (April 12, 1952), Chem Eng 59, No 5: 230-231 (May, 1952), B.I.P.C. 22:696. Dahl, Jacob, More about Norway's sulphite mill which cooks with ammonia base. Pulp Paper Ind. 20, No. 2: 65 (Feb , 1946); B I PC. 16: 369 Dieckmann, Richard "Sulfitzellstoff," page 213, Ottono, Elsner, Berln u. Doree, Charles, and Barton-Wright. C, The acid obtained from sprucewood by the action of sulphurous acid in the presence of ammonia J. Soc Chem. Ind 48, No. 2: 9-12T (Jan. 11, 1929): C.A 23: 1885, B.C.A 1929B: 166.
T A PPI
27.
28.
29. 30.
31. 32.
33.
34.
35. 36.
37.
38.
39 40 41.
42
50 .
Dorce, Charles, and all, Leshe, The hgnosulphonic acid obtained from sprucewood by the action of sulphurous acid in the presence of ammonia .. Soc. Chem. . 44, No. 23: 270-274T (June 5, 1925), C.A 19: 2742. Engelstad. Alfred, the Cross and Engelstad process for cooking cellulose with sulphurous acid solution in the presence of ammonia Papr J. 19, No. 5: 58-60, No. 6: 6769 (March 31', April 15, 19:31); C.A. 26: 4711. Fournier, Raymond, Imitation kraft by the so-called Gluteor process. Papeterie 50, No. 4: 170, 173-174 (Feb. 25, 1928), T.S. 87: 238 Frank, - -, Quality of the cellulose prepared by the Konig process. Papier-Ztg. 39, No. 17: 571 (Feb. 26, 1914); Wochbl Papterfabr. 45, No. 13: 1118-1121 (March 28, 1914); C.A. 8: 1502. Froberg, A., Konig's new process for the manufacture of cellulose Wochbl Papierfabr 44, No. 47:4432-4434 (Nov. 22, 1913);.1. Soc. Chem Ind. 32: 1152; C.A. 8: 2802. Hgglund, Erik, Chemistry of sulphite cooking. Svensk Kern Tid. 38, No. 7:177-192 (July, 1926); Papier-Fahr. 24, No. 30: 449-450; No. 32: 483-488 (July 25, Aug. 8, 1926); C.A. 20: 3807; T.S. 84: 189, B.C.A. 1926B: 312, 911. Hatch, Raymond, S , Comparison of possible bases for sulphite pulping-economics of recovery. Pulp Paper Ind. 21, No. 4: 42, 44, 46, 48 (April, 1947); Pulp Paper Mag. Canada47, No. 9:80-84 (Aug. 1946); C.A. 40: 6812; B.A. 1946B, II: 456, 1948B, 11:24; B I.P.C. 17: 153. J., Alkalies as bases for sulphite liquor. PapierFabr. 24, No. 45: 691-695; No. 46: 709-713; No. 47: 722728 (Nov. 7-21, 1926), Paper Trade . 84, No. 9: 51-60 (March 3, 1927); Tech. Assoc. Papers 10, No. 1: 130-139 (June, 1927); Pape) Ind. 8, No. 11: 1914a-1914h, 1917 (Feb., 1927); C.A. 21: 1350, .S. 85: 171. Hazelquist, Svarre E., Innovations in Sweden and Norway. Pulp Paper Ind. 20, No. 13: 58 (Dec., 1946); B.I.P.C. 17: 245. Hepher, W. S., and Jahn, . C., Action of ammonium sulphite on white fir. Paper Trade J. 95, No. 19: 33-38 (Nov. 10, 1932); C A. 27: 1748; .S. 96: 25, B.I.P.C. 3: 98. Horton, J. L, Organization and implementation of an ammonia-base mill trial. Pulp Paper Mag. Can. 54, No 3: 205-209, 214 (Convention, 1953); B.I.P.C. 23, No. 8: 584. Houghton, E. O., Ammonium bisulphite-its use as a base in the sulphite process. Pulp Paper Mag. Canada 35, No. 2: 97-101 (Feb, 1934); T.S 99: 23: C.A 28: 2896; B.C.A. 19341: 316; B.I P.C 4: 167. Howell, Charles, M., and Cunningham, Eugene, L, Iffect of chip dimensions on penetration of ammonia-base cookacid Paper de. 136 No 23: 14(June5, 1953). Huseby, . A., and Schel, M A, Corrosion and corrosion testing in the pulp and paper industry. Tappi 33, No 3 138-148 (March, 1950); B I.P C 21: 693. Jennes, L. C., and Nystrom, G. L , Sulphite semichemical pulping of chi p screenings. Tech. Assoc. Papers 31: 443445 (June, 1948); Paper Trade.1 126, No. 24: 53-55 (June 10, 1948) C A. 42: 5665, B A. 1948B, I. 389, 470; B.I.P.C 18 793. Johnstone, I . F., Recove y of sulphur dioxide from dilute gases. Pulp Paper Mag Can 53, No. 4: 104-112 (March, 1952), Pape Trade J 134, No. 21: 24, 26, 32, 36, 39 (May 2:1, 1952), 1I P.C 22: 696. Johnstone, F., Recovery of sulphur dioxide from waste gases In. Eng. Chem 27: 587-593 (May, 1935). Johnstone, . F., and Keyes, D).B., Recovery of sulphur dioxide from waste gases Ind. Eng. Chem 27: 659-665 (June, 1935). Johnstone, H. F., Read, . J., and Blankmeyer, . C., Recovery of sulphur dioxide from waste gases Ind Eng. Chem 30. 101 (Jan , 1938) Jolley, R S, Burning of sulphite liquor Pulp & Paper26, No. 10 98, 100, 102 (Sept. 1952); B.I.P.C. 23, No. 2: 128. Jonas, K. G , and Walter, P., Sulphite cooking process. Wochbl Paperfabr 62, No. 23A: 55-58 (June 6, 1931), BI.P.C. 1:36. Jones, R. M., and Detcher, T. E., Ammonia base in the neutral sulphite semichemical pulping process. Tappi 34, No. 8: 88A, 90A, 92A, (Aug., 1951); B.I.P C. 22:47 Jones, R. M., and Detcher, T. E., Ammonium bisulphite pulping Paper Trade J 133, No 5: 20, 22, 24, 26, 28 (Aug 3, 1951); Paper Mill News 74, No. 36: 12-16 (Sept. 8, 1951); Pulp Paper Mag. Canada 52. No 11:116-122 (Oct, 1951), C.A. 46: 734, B.I.P.C. 22. 54. Konig, ., asenbaumer, J , and Braun, M., Manufacture of cellulose from wood and textile fibers and utilization of the waste liquor. Z. angew. Chem. 26: 481-485 (Sept. 12, 113), . Soc Chem. Ind. 32: 939; Paper 13. No. 8: 21 (Nov. 5, 1913).
LaFond, L. A, and olzem, F., Commercial sulphite production experience with ammonia-base acid. Tappn 34, No. 6:241-247 (June, 1951); CA 45: 8764, B.A. 1951 B, II: 887, B I P.C. 21: 806. 52. Markham, Aaron, , and McCarthy, Joseph, L , Commposition changes occurring during vacuum evaporation, steam stripping. and de-ashing of ammonium sulphite liquors Tech. Assoc. Papers 31. 236-238 (June, 1948), Paper Trade J 126, No. 25: 70-72 (June 17, 1948); C.A 42: 5664; B.A. 1948, 1: 390, 535; B.I.P.C. 18 792 53. Markham, Aaron, 1 , Peniston,Quintin P..and McCarthy, Joseph, L , The pyrolvsis of ammonium sulphite waste liquor to yield ammonia. Tech. Assoc Papers 31: 407411 (June, 1948); Paper Tade 1. 127, No. 64-68 (July 1, 1948); C.A. 42: 7040 B A 1948, I: 390, B. P.C. 18 871 54. Marriner, D. E , and Whitney, Roy, P., The solubility of sulphur (dioxide in ammonia-base sulphite cooking acid. Paper Trade 126, No. 21: 52-54 (May 20, 1948); Tech. Assoc. Papers 31: 143-145 (June, 1948); C.A 42: 4748; B.A 1948B, II: 390, 535; BI.I C 18: 713. See also TAPPI data sheets 148C-148D (Dec., 1948) 55 Martin, . , Utilization of NI-lbase SO1 liquor. Tappi 36, No. 6: 175-176A (June, 1953:); Proc. 4th Ann. Pac NW Ind. Waste Conference Washington State Inst. of Tech., Washington State College 56. Marusawa, Tsuneya, Constitution and stability of various liquors used in the sulphite process and their specification in the digestion process .. Soc. Chem, Ind. Japan 20: 255-301, 737-773 (1917); .1. Soc Chem, Ind. 36: 868; 37: 52A; C.A. 11:2405. 57 McKee, Ralph HI., and Cable, Donald E., A liquid sulphur dioxide process for sulphite pulp. III. Character of pulp obtained from extracted longleaf pine chips. Paper Trade J. 80, No 17: 41-46 (April 23, 1925): C.A. 19: 1947; T.S. 81: 136. 58. Mottet, Arthur L., The sulphonation of western hemlock lignin. Pac. Pulp Paper Ind 13, No 10 22-25 (Oct., 1939), B.I.PC. 10: 121 59 Moulton, . W, and Ziegler, J. G., Study of the effect of NH, pretreatment on pulping of resinous woods. U. of Washington thesis (19:32) 6O Palmen, John, The cooking of spruce chips with sulphur dioxide solutions of high concerntiation Finnish Paper Timber .. , No 21: 612, 614-616; No. 24: 696, 698-700 (Nov. 15, Dec 31, 1926); Pulp Paper Mag. Canada 25, No 48: 1547-1551 (Sec 1, 1927), 7' S. 86: 339. 6l Palmrose. G. V., and Hull, J H., Pilot plant recovery of heat and sulphur from spent ammonia-base sulphlte pulping liquor. Tappi 35, No 5: 193-198 (May, 1952); B. P C 22: 775. 62 Peterson, C J , and Hixon, R M., The use of ammonium hydroxide as a pulping agent for the grasses. Iowa State Coll . Sci 7, No. 1: 25-28 (Oct, 1932), C A. 27. 1505. 63 Pullianell, Emo, Calciulm, sodium, ammonium, and magnesum bisulphite cooking liquors and their recovery. Finish Paper Timber .1 29, No 16: 225-226, 228-229 (August 30, 1947), B I.P.C 18: 402. 64 ayonier sulpute mill will reopen with new ammoniabase cooking system Pulp Pape lnd 19, No 7:21 (July 1945). i65Ress, Hansl The present technical position of the manutacture of sulphite pulp from pine lnd beech. ZellstoffFaser 32, No 7 97-106 (July, 1932), S. 102: 169, B I.P.C 6: 157. Process Inds 34, No. 12: 972-974 (Dec 1950); B I.P.C. 21: 357. Robak, C A. Ammonun sulphite cellulose cooking process makes headway. Ind Eng Chem. News Ed. 14, No. 9:396 (Oct. 10, 1936). B I.P C. 7: 91. Rue, John D., Soluble sulphites and their bisulphites m pulping of wood A review of the literature. Paper rade .. 81, No 16: 54-56 (Oct 15, 1925), Tech Assoc Papers9, No. 1: 137-139 (1926), 7'S 82:251 Schubert, Max, "Die Cellulose Fabikation," 3rd ed., Berlin, Fischer's Technologlscher Verlag M. Krayn Simmonds, F. A, Kingsbury, R. M , Martin, J S , and Keller, E. L., Purlfied hardwood pulps for chemical conversion. 1. Aspen sulphite and prehydrolysls-sulphite pulps. Tappi 36, No 3:103-110 (March, 1953), B I P C 23. No 8: 574. Solvay P ocess Co., Comparison of various methods of sulphite pulplng front the point of view of waste liquors. Northeastern blood Utilization Council Bull No. 7 65-72 (Oct., 1945); BI P.C 16 211. Stockman, Lennart, Cooking with ammonium bisulphite Svensk Papperstidn. 56, No. 1: 11-14 (Jan 15, 1953), B.I.P.C. 2:3, No 7 509
51.
67 68
69 70.
71
72
73
83 84
Stops. Paul, A survey of some pulping methods. Proc. Australian Pulp Paper Ind Tech. Assoc. 1: 154-165; discussion, 165-168 (Dec., 1948); B.A. 1948B, 11: 606; R I. P.C. 19: 12. Sulphite mill cooks with ammonia base in Norway; another with soda base in Sweden. Pulp PaperInd. 19, No. 10: 24 (Oct, 1945); B.I.P.C. 16: 165. Sulphite pulp may offer postwar ammonia market. Chen. Ind. 55, No. 5: 818 (Nov., 1944), B I.P.C. 18: 186. Svenska Pappers- och Celluloseingenidrsforeningen. Pulping of wood with ammonium bisulphite according to Engelstad Tekniska Meddelanden TB 2 (June, 1940), 1 page. Thode, E F., and Lee, Y. H., Ammonium-base sulphite pulping of hardwoods. Tappi 33, No. 6: 257-260 (June, 1950; B I.P.C. 20: 816. Tucker, F.. Digester linings for soluble-base sulphite pulping Tappi 33. No. 1: 29-32 (Jan., 1950); B.I.P.C. 20: 393. Vincent, Rex , Position of the sulphite (acid) process in the chenmcal and paper helds (industrial review) and bibliography. Also evaporation of liquors, hardwoods. Paper Tr ade .1. 122, No 9: 136, 138, 140, 142; T S 93-96 (Feb. 28, 1946), Tech. Assoc. Papers 29:202-205(June, 1946), Paper l News 69, No. 9: 122, 124, 126-127 (March 2, 1946); Pulp Paper Ind. 20, No. 3: 50, 52 (March, 1946); Papermaker 111, No. 5: TS. 54-56 (May, 1946); C.A. 40: 2299, B.I.P.C 16:370. Waddell, R D, Ammonia-base process-evaporating and burning at Lebanon Pulp & Paper 25, No 11: 58 (Oct. 1951); B I.P.C. 22: 205. Waddell, R D., Ammonia-base sulphite mill. Pulp & Paper25, No. 8: 56, 58 (July, 1951); B I.P.C. 22: 205. Wausau's new acid plant in full operation. PaperTrade J 136 No. 23: 10 (June 5, 1953); Paper Mill News 72, No 23: 6 (June 6, 1953); Paper Ind. 35, No. 4: 423-424 (July. 1953) Whitney, Roy P , and I, S. T, Design basis for ammonia-base sulphite raw-acid towers. app 35, No. 12: 569-576 (Dec. 1952), B I P C. 23: 309. Whittemore, E. R, Divden, E. C., and Aronovsky, S. I., Conductometric analysis of sodium sulphite and ammoniacal pulping liquors Paper Trade J. 112, No. 25: 29-34 (June 19, 1941); CA 35: 6537; B.C.P.A. 1941B, I1: 340; B.I.P.C. 11:396. Yorston, F. H., Use of ammonia in sulphite cooking. Pulp PaperRes Inst. Canada. Laboratory Rept. No. 27 (1943-44).
109.
1923 Cross, Charles F, and Engelstad, Altred, Wood pulp. Brit. pat. 229,002 (Nov. 15, 1923); Ger. pat. 495,146 (Oct 23, 1924); Fr. pat. 588,071 (Oct. 25, 1924), C.A. 19: 3018: T.S. 82: 251. 1925 Cross, Charles, F., Manufacture of wood pulp and byproducts. U. S. pat. 1,547,907 (July 28, 1925); C.A. 19: 3018; T.S. 82: 235. 1927 Billwiller, John, Method of loosening vegetable fibers. U. S. pat. 1,649,281 (Nov. 15, 1927); T.S. 87: 238; C.A. 22: 500. Ekstrom, P. G., and Hult, R H., Process for the manufacture of sulphite pulp from wood or other fibrous materials. Swed. pat. 68,741 (Sept. 26, 1927), T.S. 91: 275. 1929 Michael, Wilhelm, and Palm, Albert, Recovery of sulphite waste liquor for re-use. U. S. pat 1,723,800 (Aug. 6, 1929); Can. pat 28:3,415 (Sept. 18, 1929), TS 89: 92; 91: 207; 92: 31; C.A. 22: 4246. Richter, George, A., Recovery of valuable products from spent sulphite liquors. U. S. pat 1,710.272 (April 23, 1929); T.S. 90: 204; C.A. 23: 2780. Sido, Otto, and Wiederhold, Hermann. Process for the production of cellulose. Ger. pat. 505,589 (Aug. 18, 1929); T.S. 93: 174; C.A. 25: 593. 1930 Baker, Webster E. B., Sulphite wood pulp and method of making the same. U. S. pat. 1,773,419 (Aug. 19, 1930); C.A. 24: 5158. Richter, George A., Production of sulphite pulp. U. S. pat. 1,780,842 (Nov. 4, 1930); Can. pat. 283,024 (Sept. 4, 1928); T.S.89:81; 92:292; C.A 25:206. 1931 Benson, Henry, K., Process for making sulphite pulp from Douglas-fir and other resinous conifiers. U. S. pat. 1,805799 (May 19, 1931); C.A. 25: 3825; T S. 94: 126. Hixon, Ralph M., Peterson, Charles J., and Werkman, Charles H., Process of pulping plant tissues by means of a volatile base. U. S. pat. 1,802,715 (April 28, 1931); T.S. 94: 123; C.A. 25:3836. Richter, George A., Process for the production of chemical wood pulp. U. S. pat. 1,817,525 (Aug. 4, 1931); Can. pat. 309,867 (March 31, 1931); T.S. 93: 170; 94: 139; C.A. 25: 5560. 1932 Richardson, Roger V., Pulping process. U S. pat 1,885.764 (Nov. 1, 1932); Can. pat. 335,222 (Aug. 29, 1933); T.S. 97: 233; 98: 198; C.A. 27: 5538. Richardson, Roger W.. and Sherman, Clarence S., Production of cellulose pulps. U. S. pat. 1,851,522 (March 29, 1932); Can. pat. 328,828 (Dec 27, 1932); T.S. 95: 204; 97: 318; C.A. 26:3112. Seaman, Stewart E., Process of producing cellulose. U. S. pat. 1,891,337 (Dec 20, 1932); Can. pat 326,709 (Oct 11, 1932); T S 97:234, 295; C.A 27:2032. 1933 Bori, Antonio B., and Estape, Jos6 M., Process of cellulose. U. S. pat. 1,920,239 (Aug. 1, 1933), 232; C.A. 27: 4926. Hahn, Frederick C., and Fothergill, Robert E., ture of wood pulp. U. S. pat. 1,926,002 (Sept T.S. 98: 198; C.A. 27: 5538 preparing T.S. 98: Manufac5, 1933);
110.
111. 112.
113.
114. 115.
116. 117.
118 119.
120
1902 Braun, Deutsches Republic pat 151,285 (1902). 1912 Konig, J., Manufacture of a cattlefood, with simultaneous recovery of cellulose, resin, etc., from cellulose containing material Ger pat. 265,483 (Feb. 15, 1912); J. Soc. Chem Ind 32:1063; C.A 8: 386. Konig, J, Fodder and cellulose. Ger pat. 273,094 (June 14, 1912); C A. 8: 2586. Sammet, Charles, F., and Merrill, Jason L., Process for treating fiber-yielding materials. U. S. pat. 1,016,178 (,Jan. 30, 1912); C A. 6: 803. 1914 Brech, Leon, and Tyborowski, Edmund, Manufacture of cellulose from raw materials containing cellulose fiber U. S pat. 1,100;519 (June 16, 1914), Can. pat. 145,860 (Feb 11, 1913); Brit plat. 5552 (March 6, 1911); Fr. pat. 438,130 (March 6, 1911); Ger. pat. 252,321 (Feb. 23, 1911) and 257, 544 (Dec. 17, 1911); C.A. 7: 549, 1609, 2473. Harnist, Charles, Fr. pat 156,777 (1914). 1917 Marusawa, Tsuneya, Process of manufacturing paper pulp U S. pat. 1,244,525 (Oct 30, 1917); Jap. pat. 31,675 (Oct. 27, 1917); and 31,941 (Dec 24, 1917); C.A. 12: 224, 1252, 2249. 1921 128. 129. 1922 Billwiller, John, and Billwiller, J., Manufacture of fibrouscontaiing substances. Brit. pat 206,570 (Aug. 4. 1922); Ger. pat :376,488 (Nov. 11, 1919); T.S. 77: 125, 79: 17; J. Soc Chemn. Ind 4:; 1190, CA. 18: 1199. 121. 122.
102. 103.
123.
104.
124. 125.
105 106
126. 127.
1934 Estape, Jos6 M., Production of alpha-cellulose. Fr pat 759 690 (Feb. 7, 1934); T.S. 99: 332. Richardson, Roger W., Recovery of ammonia from cook liquor. U. S. pat. 1,943,345 (Jan. 16, 1934); Can. pat. 353,924 (Nov. 5, 1935); T.S. 99: 164; 103: 248; C.A. 30: 1561. 1935 Brill, John L., Ammonia recovery. U. S. pat. 2,014,374 (Sept. 17, 1935); C.A. 29: 7597. Kuwahata, Seiji, Pulp for rayon. Jap. pat. 11,240 (April 6, 1935); C.A. 29: 83:30; T.S 103: 70. 1936 Norsk Hydro-Elektrisk Kvaelstofaktieselskab, Recovery of sulphur dioxide and ammonia from sulphite waste liquors. Nor. pat. 59,627 (May 6, 1936); Swed. pat 92,828 (Oct. 11, 1937); C.A. 33: 1938
108
130.
131. 132.
Richter, George A., Fiber-liberating process. U. S. pat. 2,032,437 (March 3, 1936); C.A. 30: 2759; T.S. 103: 248. Richter, George A., Process of correlating chemical recovery in pulp mills operating with different kinds of liquors. U. S. pat. 2,047,032 (July 7, 1936); C.A. 30: 6197; T.S. 103: 354. 1937 Norsk Hydro-Elektrisk Kvaelstofaktieselskab, Recovery sulphur dioxide and ammonia from waste liquors. Nor. pat. 58,194 (July 19, 1937); C.A. 31:8926. Olsen, Fredrich, Cellulose pulping system and product thereof. U. S. pat. 2,087,263 (July 20, 1937); C.A. 316464; T.S. 106: 130; B.C.P.A. 1940B: 199. Saft, Juljusz, Cellulose. Fr. pat. 817,852 (Sept. 13, 1937); C.A. 32: 2351. 1938 Kovats, Lajos, Pulp. Hung. pat. 119,466 (Nov. 15, 1938); C.A. 33: 3149. Norsk Hydro-Elektrisk Kvaelstofaktieselskab, Working up waste ammonium bisulphite liquors. Nor. pat. 59,229 (April 11, 1938); addition to 58,781 (Jan. 3, 1938); C.A. 32: 7264. Norsk Hydro-Elektrisk Kvaelstofaktieselskab, Sulphite waste liquor treatment. Fr. pat. 823,778 (Jan. 26, 1938); T.S. 109: 62. Waeser, Bruno, Pulping cellulosic material. Ger. pat. 658,686 (April 11, 1938); C.A. 32: 6462. 1939 Richter, George A., Cellulosic material pulping process. Can. pat. 382,892 (July 25, 1939).
141.
1941 Olsen, Fredrich, Goff, Lionel, and Sheldon, Lyle M., Process of producing wood cellulose. U. S. pat. 2,230,119 (Jan. 28, 1941); C.A. 35: 3090. 1942 Sheldon, Lyle, M., Cellulose pulping system. 2,300,733 (Nov. 3, 1942). U. S. pat
142
143.
1950 Jesseph, Donald C., Stable bituminous emulsion and preparation thereof. U. S. pat. 2,494,708 (issued Jan. 17, 1950). 4 claims. C.A. 44:3706; B.I.P.C. 20:768. 1951 Parrett, Arthur, N.. Wood pulp digestion. U. S. pat 2,564,028. Filed Jan. 17, 1946. Issued Aug. 14, 1951 3 claims. Assigned to Rayonier, Inc., (Cl. 92-11); B.I.P.C. 22: 87. 1952 Andersen, Carl C., Treatment of waste sulphite liquor Can. pat. 481,243. Filed Aug. 21, 1939. Issued Feb 19, 1952. 2 claims. Assigned to Norsk Hydro-Elecktrisk Kvaelstofaktieselskab; B.I.P.C. 22: 643. Helleur, Dotiald, Treatment of the spent cooking liquor ol an ammonia-base sulphite pulping process. U. S. pat 2,596,241. Filed Dec. 20, 1948. Issued May 13, 1952 4 claims. Assigned to Price Brothers & Co., Ltd. (Cl 23-129); B.I.P.C. 22: 799.
144
145.
146.
. .MEMORANDUM
Date
May 13,
1954
About a year ago it was decided that a thorough review of the literature should be made with respect to all aspects of ammonia and ammonia compounds as pulping agents. It was further decieed that this review should lead to two reports--the first report classifying the relevant literature on a subject basis, and a second report reviewing the literature critically-for the purpose of pointing up the inadequacies in our knowledge and understanding of ammonia and ammonia compounds as pulping agents, and thus outlining areas for future investigation and research in this field. Don Helleur of the Pulping Group was assigned this literature work. In August, 1953, the first report was completed and subsequently published (TAPPI 37, no. l:177A-182A(Jan., 1954)). That paper is included in this project file as Project Report i A report dealing with the second phase of the literature survey was completed about the end of 1953, and is included in the file of this project as Project Report 3
djm/jh
FORM 73
FORM 73
The first
patent was issued to Braun in 1902 (34, 69, 100). In recent years, not only has it been receiving increasing attention and interest but it has also been used fairly extensively to produce commercial tonnages of pulp. The major part of this use and interest has centered around the ammonium bisulphite process. To aid those who are interested in the literature of this particular field, references have been collected and classified for the period 1900 to June, 1953. In classifying these references, an attempt has been made to anticipate the interests of both the operational and technical approaches to the subject. No attempt has been made to review the material critically. Reference numbers below 100 are for technical papers and those above 100 are for patents.
APPLICATION TO SPECIFIC FIBROUS Woods MATERIALS
Some of these studies were directed to certain wood species generally considered difficult to pulp with calcium bisulphite liquors. For example, in the case of Douglas-fir, chips were pretreated with ammonium hydroxide to extract resinous materials, then ammonium bisulphite liquor was added to cook the wood (10). Studies on Douglas-fir without pretreatment include (11), (18), and (58) Specific wood species used to study the process variables include: white fir (36); aspen, in attempt to yield a purified pulp for chemical conversion (70); longleaf pine, using an extraction with liquid sulphur dioxide followed by the ammonium bisulphite process (57); pine and beech (65); mixed hardwoods (birch, maple, beech) using the ammonia neutral sulphite and the bisulphite processes, with base comparisons (77); Bordeaux pine (15).
Agricultural Residues
Kon Process. Wood is heated with ammonium hydroxide and this treatment is followed by treatment with a mineral acid (or vice versa ) (101); a further patent with the emphasis on by-product recovery was (102). Disadvantages of this process are discussed in (31) and general comments given in (30, 31). Gluteor. The principle of the process lies in the saponification of casein to obtain a product which under certain conditions of pressure and temperature evolves nascent ammonia which can be used for cooking fibrous materials. Merits and demerits are discussed in (8, 29). Billwiller. A broad patented process making use of such cooking chemicals as ammonia, sodium carbonate, hydrogen sulphide, etc., with the emphasis on the use of catalysts and of a pretreatment using these chemicals followed by known cooking processes (i.e., prior to 1919) (108). For the use of ammonium hydroxide specifically, see (111). Discussion of. merits (12) and general process (6). Other Processes. Pulping agricultural residues (119). See also (II, IV, V, VI) under miscellaneous cooking processes. Pretreatments with ammonium hydroxide (116) plus preferably some ammonium sulphite (120) to remove resinous materials (118) followed by the ammonium bisulphite process (10, 121, 140); or followed by sulphuric acid (50). See also (X) under miscellaneous.
Ammoniu Sphite (Neutral and Alkaline)
The first patent by Braun (100) described a more or less neutral sulphite pulping process. Comments on this process (25). Another patent is (105). A later patent tended to the more alkaline side (34, 104). One tending to the acid is (106). Pulping of straw and wood (15). Reviews covering this type (as well as those in the acid range) are (34, 68,73). Its use in semichemical pulping (48). See also (I, III, IV, VI) under miscellaneous.
Ammon Bisulphite (Excess Sulphurous Acid)
Short study using ammonium sulphite neutral process on straw (15); bisulphite on straw (7) with base comparisons; use of ammonium hydroxide on various materials (corn, oats, and straw stalks) (8, 62,102, 119).
D. E HELLEUR, Technical Associate, The Institute of Paper Chemistry, Appleton, Wis.
Cross (and Englestad) Process. Using low combined sulphur dioxide (0.5 to 0.25%) (109, 110); laboratory studies on this process are (22), and general reports (28, 76); references made to it in the studies of Doree and Hall (26, 27). Others are (106, 112, 117, 118, 121, 122, 125, 129,
177 A
T A PPI
January 1954 .
131,134, 140, 141, 142, 143, and 146). See also (I, IV, VI, IX, X, XIII) under miscellaneous. Using a liquid sulphur dioxide pretreatment (on longleaf pine) followed by the bisulphite (57). Comments on this study (65); others (7, 10, 11, 20, 35, 38). General reviews covering the process are (17, 34, 38, 85).
Miscellaneous Cooking
bases including ammonia (63); an industrial review of the sulphite (acid) process including evaporation of liquors (ammonium included) (79); comparison of the various sulphite pulping methods from the point of view of the spent liquors (71).
Evaporation
Under pressure to recover chemicals (130, 133). allied subject is concentration by recycling (144).
Evaporating and Burning (Recover) of Heat)
An
(I) Gaseous Cooking. Sammet and Merrill treat fibrous materials with gaseous ammonia and sulphur dioxide and steam (103); a gaseous pretreatment laboratory trial (16). (II) Using ammonia and steam only, there are (76,
139).
Included with a cooking process in heat recovery step (144, 146); commercial trials are reported (14, 33, 46, 61, 81).
Recovery of Cooking Chemicals
(III) A somewhat novel way of arriving at an ammonium sulphite cooking liquor is to treat a calcium bisulphite solution with ammonia, thus forming an ammonium sulphite solution with the precipitation of calcium sulphite. The fibrous material is then cooked with this ammonium sulphite liquor (104). (IV) A very broad patent covering a wide pH range, and using such chemicals as ammonia, sulphur dioxide, steam (separately or together) is (107). (V) On processes using a solution of cyanide or cyanate which forms ammonia by saponification with water; supposedly, the difficulties in the decomposition of wood by ammonium hydroxide are thereby avoided (115). (VI) Another very broad patent covers pulping with ammonia and sulphur dioxide as well as the sulphite, sulphate, carbonate, and sulphide salts of ammonium either separately or in combination; for certain wood the ammonium bisulphite is preferred; for materials like cotton linters, ammonia; agricultural residues, slightly alkaline ammonium sulphite; a "kraft" cook also can be used, e.g , 2% ammonia and 2% ammonium sulphide; etc. (128). (VII) To avoid the high cost of ammonia, Richter advocates cooking with 1 to 8% ammonium sulphate and 3 to 8% free sulphur dioxide (117). (VIII) Processes cooking with mixtures of other bases (e.g., NaOH, Na 2S, Na acetate, etc.) together with ammonia are (124, 126) (IX) To cook with a high percentage of sulphur dioxide (5 to 26%) an aqueous solution of ethyl alcohol was employed, to which was also added 0.7% ammonia (60). (X) Another process pretreats with excess liquid ammonia, the excess being removed to be followed by a solution of sulphurous acid, such that in effect the final cooking is done by the usual bisulphite process (131). (XI) Another suggests cooking with ammonium sulphate with the addition of organic nitrogen compounds-e.g , aniline, triethanolamine, etc. (135). (XII) Another in the same vein suggests using ammonium hydroxide together with mixtures of soaps, oils, fats, alkalies, sodium sibeate, potassium chloride, etc. (186). (XII1) A process re-using spent liquors after fortification with cooking chemicals is (144).
SPENT LIQUORS-UTILIZATION Recovery in General
liquor (21, 132), with magnesium oxide as the base (146), by pyrolysis (53, 71, 137), by ion exchange (deashing) (52), by steam stripping (52), and by vacuum evaporation (52). Sulphur Dioxide. Commercial trials, sulphur dioxide liberated during the burning step (14,61,81); recovered during evaporation (130, 133). Ammonia and Sulphur Dioxide Processes claiming to recover both: Solvay process (71, 133); by boiling under pressure at approximate 40% concentration (137); by boiling to liberate sulphur dioxide, then addition of a base to liberate ammonia (133); by a process of pyrolysis on the concentrated solution or the dry solids (138); pertinent to this latter process is (53); treating with magnesia to liberate ammonia and to convert liquor to magnesium base, evaporating and burning the converted liquor to yield magnesia for reuse and sulphur dioxide, which is recovered from the combustion gases using the liberated ammonia (146).
Other Liquor Utilization
Fertilizers-(5, 55). A general discussion of producing ammonia for fertilizers from wood waste is (66); liquor neutralized with basic calcium phosphate rock, etc.. evaporated and dried (114); as an organic cation exchanger (145); stabilizer in bituminous emulsions (143); re-using the spent liquor i cooking operations after fortification with cooking chemicals (144); fermentatzon to ethanol (1). Miscellaneous uses of the spent liquor are adhesives, wetting agents, dispersants, soil conditioner, yeast nutrient, etc. One such product is sold under the trademark Orzan (23, 55). A process purports to produce decomposition products by neutralizing the liquor with ammonia, and heating with carbon to yield acetic, formic, and oxalic acids and activated carbon (113).
MILLS AND OPERATIONS
Literature references to mills that are using or have used ammonium-base processes either on full-scale operations or as short mill trials are listed below. Except for one in Norway, the mills listed are in the United States:
1. American Box Board Co, Filer City, Mich. (48). 2. Consolidated Water Power &Paper Co, Wisconsin Rapids,
Wis., and Interlake Div, Appleton, Wis. (2, 46, 48)
3 4. 5. 6. 7 8. 9.
Crown Zellecbach Corp , Lebanon mill (also pilot plant study of evaporation and burning the spent liquor) (1, 51, 61, 81) Diamond Match Co , Ogdensburg mill (37). Eastern Corp., Lincoln and South Brewer mills (51). International Paper Co , Southern Kraft Div. (48). Rayonier, Inc., Shelton, Wash (3, 5, 33, 51, 65). Toten Cellulosefabrik, Nygard (Norway) (24, 35, 51, 75). Wausau Paper Mills Co., Brokaw, Wis. (2, 82).
2 3. 4.
5. 6.
base trial discussed (34). Design of ammonia-base sulphite acid systems (42, 43, 44, 45,54, 82,83). Preparation of raw cooking acid (13) Digester linings (78). Corrosion of linings (40). Review of the field and a report of the progress (48, 49, 65, 72, 75).
ANALYSIS, TESTING, AND GENERAL CHIEMISTRY
7.
rose method (13). Conductometric analysis of the pulping liquors for such as ammonium hydroxide, carbonate, sulphite, bisulphite, and acetate (84). Sulphite process (22, 26, 27, 32, 36, 56, 58) Chemistry of reactions, cooking variables, etc., kinetics of, penetration studies (16, 19, 36, 39); ammonia pretreatment (16, 59); system: ammonia, sulphur dioxide, and water (42, 43, 44, 45); cooking liquor (56); spent liquor (27, 32).
ADVANTAGES CLAIMED FOR AMMONIA-BASE PULPING
8. 9 10.
11.
12. 13
Claims and comparisons together with their references are listed below. Many of these claims, it will
be noted, are not specific to ammonia-base but exist only when taken in comparison with some other base. Practically all the claims are made with respect to the ammonium bisulphite process. 1. Ease of raw material handling (i.e., cooking chemicals) (4, 37). 2 Amenable to the pulping of difficult woods (9,
10, 11, 18, 58).
14 15.
16.
3. Superior quality of raw acid (4, 37, 54). 4. Superior condition of the digester equipment (4). 5. Cooking variables (4, 58, 77); superior penetration (9, 19, 74, 81); lower cooking temperatures (24,
35, 67, 72, 81); reduced cooking time (28, 37, 67).
17.
6.
18
17, 22, 24, 35, 37, 51,58, 67, 72, 74, 77, 81). 7. Superior pulps qualities, high alpha-cellulose (10, 41); stronger pulp (4, 9, 38, 41, 51, 74, 81)
19 20 21. 22.
8.
9.
10. Recovery of heat and chemicals (14, 24, 35); and all of section "Spent Liquors-Utilization."
GENERAL RE VIEWS
have been incorporated in the above. For ready reference, they are (34, 37, 68, 75, 79, 85).
LITERATURE CITED References to the Bulletin (Library Notes) of The Institute of Paper Chemistry (B.I.P.C.) and Chemncal Abstracts (C. A.) are included in all cases where the abstract gives a summary of the article in question. 1. Agar, Hilda, P., and McCarthy, Joseph, Sulphite waste liquor. I. Fermentation of ethanol of cone. Ca. Mg, and
.
23 24. 25 26
NI14 sulphite waste liquor. Tappl 34, No 3: 126-131 (March, 1951); B.I P.C. 21:584; CA 45:4447. Ammonia in more mills; liquor burning at Badger and Interlake. Pulp & Paper 25, No 3: 64 (Match, 1951); B.I.P.C. 21: 585. Ammonia pulping report. Paper Ind 33, No 12: 14381439 (March, 1952); B.I.P.C. 22: 614. Aries, Robert S., Recent developments in the utilization of sulphite waste liquors. Northeastern Wood Utilization Council Bull. No. 14- 97-121 (Jan., 1947), B.I.P.C. 17: 380. Aries, Robert S., Research on lignin as a soil builder Northeastern Wood Utilization Council Bull No. 7: 56-62 (Oct., 1945'; C.A. 40:1623; B.I.P.C. 16: 183. Arnot. J. Melrose, Some new processes for the separation of fibrous cellulose from plant substances. l Wod's Pape7 Trade Rev. 95, No. 11: 961-962, 964 (March 13, 1931), B .P.C. 1, No. 9: 20. Aronovsky, S. I., Ernst, A J . Sutcliffe, H. M , and Nelson, G. H.. Agricultural residue pulps-compatison of pulping processes Tech. Assoc Papers 31: 299-304 (J, 1948), Paper Trade J. 126, No. 26: 78-83 (June 24, 1948); C.A. 42: 5662; B.A. 1948B, IT: 387; B I P C 18: 790. Barbier, Emile, Imitation kraft paper hoin stiaw by means of the so-called Gluteor process. PapeteTe 49, No. 12: 538-543 (June 25, 1927); T.S. 86: 7; C.A. 21: 2984 Benson, Henry, K, Ammonia pulping of wood Pulp & Paper24, No. 8: 74, 76 (July, 1950), B I.P.C. 20 907. Benson, H K., Erwin, R. P., Hendrickon, .1. R., and Tershin, J. A., The pulping of Douglas-fir by ammonia-base liquor. Paper Trade J. 99, No 12- 87-89 (Sept 20, 1934); Tech. Assoc. Papers, 18: 513-515; discussion, 486-487 (June, 1935): C.A 28- 7522; T.S 99: 322; B I P.C. 5- 46 Benson, H. K., and Lucas, J. E, The pulping of Douglasfir with ammonium bisulphite. Paper Trade . 111, No. 7: 32-34 (Aug. 15, 1940); C A 34:8265, B.C.P.A. 1940B: 786; BIP.C. 11:35. Billwiller cooking process. Zellstoff u. Paper 11, No. 4: 197 (April, 1931), T S. 94:3. Bishop, F. F., and Honstead, J F, Ammonia-base sulphite pulping liquors-their preparation and analysis. Tappt 34, No 7:318-323 (July, 1951); C.A 46:255; B.A 1951B, I: 1009: B I.P C 21: 877. Booth, Kenneth, C , Ammonia sulphite process Pulp & Paper 26, No. 9: 80, 82, 84 (Aug, 1952); B I P C 23. 754. Brot, M. V., and Hirschel, M., Treatment of straw and of resinous woods with sodium sulphite and ammonium sulphite. Paper 29, No I: 75-80 (Jan., 1926); Paper Ind 8, No. 1: 97, 99, 101 (April, 1926); T.S 83: 100, C.A. 20 1322. Bryde, 0 , The significance of penetration in the sulphite cook; the possibilitv for improving penetration by artificial means. Norsk Skogind. 3, No 7:169-172 (July, 1949); R.I.P.C. 20: 192. Cable, Donald, E, Sulphite pulp from spruce Paper Trade .. 85, No 13: 43-49; No. 14: 58-63; No 15 50-55 (Sept, 29, Oct. 6, 13, 1927); Pulp Paper Maq Canada 25, No. 39: 1215-1222; No 41: 1299-1305; No. 42- 13311332; No. 44: 1405-1408, 1422, 1424 (Sept. 29, Oct. 13, 20, Nov 3, 1927); Zellstoff u. Pape 8, No. 6 372-373 (June, 1928); .S. 87: 28, C A. 22 1681. Chidester. G ., and McGovern, J. N , Sulphite pulp from Douglas-fir Paper Tae . 113, No. 9: 34-38 (Aug. 28, 1941); Tech. Assoc Papers 24: 226-230 (June. 1941), Paper Ind 28, No. 3. 288 (June, 1941), B I P C 12 57 Christensen, G. N , and Williams, E J , Diffusion in Wood III. Ion selection and its effect on the diffusion ol electrolytes. Austialan .f. Applied Sr 2 440-453 (1951) Colter, John, S, Use of recovered ammonia in sulphite pulping. Paper Trade.. 136, No 23 13 (June 5, 1953) Cooper, Stuart, R Ammonia recovery from sulphite waste liquor. Paper Trade. 136, No 23 13 (Juni 5, 1953). Cross, C. F., and Engelstad, A, The action of aqueous sulphurous acid on lignocellulose. II. .. Soc Chem Ind 44, No. 23: 267-270 (June 5, 1925); Paper Trade 81, No. 8:45-48 (Aug 20, 1925); T S 82:8; CA 19:2742. Crown Zellerlach Corp. Add waste utilization Chem Week 70, No 15 34 (April 12, 1952); Chem Eng. 59, No 5: 230-231 (May, 1952), B I.P.C. 22 696. Dahl, Jacob, Moie about Norway's sulphite mill which cooks with ammonia base Pulp Paper lnd 20, No 2: 65 (Feb, 1946), B I P.C. 16: 369. Dieckmann, Richaid "Sulfitzellstoff," page 213, Ottono, Elsner, Berlin Pub. Doree, Charles, and Barton-Wright, Eustce, C , The lignosulphonic acid obtained from sprucewood by the action of sulphurous acid in the presence of ammonia Soc Chem. Ind 48, No 2: 9-12T (Jan 11, 1929): C A. 23: 1885, B.C A 1929B: 166. 179 A
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Paper Trade .. 126, No 21: 52-54 (May 20, 1948); Tech. Assoc. Papers 31: 143-145 (June, 1948); C.A. 42: 4748; B.A 1948, : 390, 535, B .P C 18: 713 See also TAPPI data sheets 148C-148D (Dec., 1948). 55 Martin, .1 B., Utilization of NH-hbase SOa liquor. Tappz 36, No 6: 175-176A (June, 1953); Proc. 4th Ann. Pac. NW Ind Waste Conference Washington State Inst. of Tech., Washington State College 56 Marusawa, Tsuneya, Constitution and stability of various liquois used in the sulphite process and their specification in the digestion process .. Soc. Chem Ind Japan 20: 255-301, 737-773 (1917), .. Soc. Chem, Ind. 36: 868; 37: 52A, C.A. 11:2405. 57. McKee, Ralph H., and Cable, Donald E., A liquid sulphur dioxide process for sulphite pulp. III. Character of pulp obtained from extracted longleaf pine chips. Paper Trade J 80, No. 17: 41-46 (April 23, 1925); C.A. 19: 1947; T.S 81: 136. 58 Mottet, Arthui L, The sulphonation of western hemlock lignin Pac Pulp Paper Ind. 13, No 10: 22-25 (Oct., 1939); B.l P C. 10- 121. 59 Moulton , R W, and Zieglem, J G , Study of the effect of NI-[ pretreatment on pulping of resinous woods. U. of Washington thesis (1932). alinen, John, The cooking of spruce chips with sulphur Finnish Paper dioxide solutions of high concentration Timber .. 6, No 21: 612, 614-616, No. 24: 696, 698-700 (Nov. 15, Dec 31, 1926); Pulp Paper Mag. Canada 25, No. 48 1547-1551 (Sec. 1, 1927); T' S. 86:339. 61. Palmrose. G. V, and Hull, J. H., Pilot plant recovery of heat and sulphur from spent ammonia-base sulphite pulping liquor. Tappi 35, No. 5: 193-198 (Mav, 1952), B I.P.C. 22: 775. 62 Peterson, C J., and Hixon, R M., The use of ammonium hydoxide as a pulping agent for the grasses. Iowa State Coll J. Sciu7, No 1: 25-28 (Oct, 1932), C A. 27:1505 Pullianien, Eino, Calcium, sod, u, ammonium, and mag63 nesium bisulphite cooking liquors and their recovery Finnsh Papel Timbe, J. 29, No. 16: 225-226, 228-229 (August 30, 1947); B.l.P.C. 18: 402. 64 Rayonier sulphite mill will reopen with new ammoniabase cooking system Pulp PaperInd 19, No 7:21 (July 1945). Ress, Hans. The present technical position of the malul65 Zellstofffacture of sulphite pull) from pine and beech Faser 32, No. 7: 97-106 (July, 19:32); T.S 102: 169, B I P C 6: 157. Process Ilds. :34, No. 12- 972-974 (I)e., 1950), H 1.P (C 21: 357. Roak, C. A Ammonium sulphite cellulose cooking pi ocess makes headway Ind. Eng Chem News Ed. 1-I, No 9:396 (Oct 10, 1936), B.I.P.C. 7: 91 Rue, John D., Soluble sulphites and their bisulphtes in Paper pulping of wood A review of the literature Trade . 81, No. 16: 54-56 (Oct. 15, 1925); Tech Assoc Papeis9, No. 1: 137-139 (1926), T S. 82- 251 Schubert, Max, "Die Cellulose Fabrikation," 3rd ed, Berlin, Fischer's Technologischer Verlag M. Krayn Simmonds, F A , Kingsburv, R M., Martin, J S , and Keller, E L,, Purified hardwood pulps for chemical con1. Aspen sulphite and prehydrolysis-sulphite version pulps Tappi 36, No. 3 103-110 (March, 1953), B I P.C 23. No. 8: 574. Solvav Process Co., Comparison of various methods of sulphite pulpiig from the point of view of waste Northeastern Wood Utilizaton Counczl Bull. No. 7: 65-72 (Oct, 1945); B.I P.C. 16: 211. Stockman, Lennart, Cooking with ammonium Insulphlte. Svensk Papperstidn. 56, No 1- 11-14 (Jan. 15, 1953), .I P C 23, No. 7:509 Vol. 37, No. I January 1954
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Stops Paul, A survey of some pulping methods. Proc. Austrahan Plp Pape Ind. Tech. Assoc 1: 154-165; discussion, 165-168 (Dec., 1948); B A. 1948B, 11: 606; ?BI. PC. 1): 12 Sulphite mill cooks with ammonia base in Norway; another with soda base in Sweden. Pulp PaperInd. 19, No. 10: 24 (Oct, 1945); B.I.P.C. 16: 165. Sulphite pulp may offer postwar ammonia market. Chem. Ind. 55, No. 5: 818 (Nov., 1944); B.I.P.C. 18: 186. PulpSvenska Pappers-och Celluloseingeniorsforeningen. ing of wood with ammonium bisulphite according to Engelstad. Tekniska Meddelanden TB 2 (June, 1940), 1 page. Thode, E. F., and Lee, Y. H., Ammonium-base sulphite pulping of hardwoods. Tappi 33. No 6: 257-260 (June, 1950, B.I.P.C 20:816 Tucker, E. F., Digester linings for soluble-base sulphite pulping. Tappi 33. No. 1: 29-32 (Jan., 1950); B.I.P.C 20 393. Vincent, Rex., Position of the sulphite (acid) process in the chemical and paper helds (industrial review) and bibliography. Also evaporation of liquors; hardwoods. Paper Trade J 122, No 9: 136, 138, 140, 142, T.S. 93-96 (Feh 28, 1946); Tech. Assoc. Papers 29:202-205 (June, 1946); Paper Mill News 69, No. 9: 122, 124, 126-127 (March 2, 1946), Pulp Paper Ind. 20, No 3: 50, 52 (March, 1946); Papermaker 111, No. 5: T.S. 54-56 (May, 1946); C.A. 40: 2299; B.I.P.C. 16:370. Waddell, R. D., Ammonia-base procesa-evaporating and burning at Lebanon. Pulp & Paper 25, No. 11: 58 (Oct. 1951); B.I.P.C. 22: 205. Pulp & Waddell, R. D, Ammonia-base sulphite mill Paper25, No. 8: 56, 58 (July, 1951); B.I.P.C. 22:205. Wausau's new acid plant in full operation. Paper Trade J 136, No. 23: 10 (June 5, 1953); Paper Mill News 72, No. 23: 6 (June 6, 1953); PaperInd. 35, No. 4: 423-424 (July. 1953) Whitney, Roy P., and Han, S. T., Design basis for ammonia-base sulphite raw-acid towers. Tappi 35, No 12: 569-576 (Dec 1952); B I.P.C. 23: 309. Whittemore, E R., Dryden, E. C, and Aronovsky, S. I., Conductometnc analysis of sodium sulphite and ammoniacal pulping liquors. Paper Trade J. 112, No. 25: 29-34 (June 19, 1941); C A. 35: 6537; B C.P.A. 1941B, TI: 340; B.I.P.C. 11:396. Yorston, F. H., Use of ammonia in sulphite cooking. Pulp Paper Res. Inst Canada. Laboratory Rept. No. 27 (1943-44).
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1923 Cross, Charles F , and Engelstad, Alfred, Wood pulp. Brit. pat. 229,002 (Nov. 15, 1923); Ger. pat. 495,146 (Oct 23, 1924); Fr. pat. 588,071 (Oct. 25, 1924); C.A. 19: 3018; T.S. 82: 251. 1925 Cross, Charles, F., Manufacture of wood pulp and byproducts. U. S. pat. 1,547,907 (July 28, 1925); C.A. 19: 3018; T.S. 82: 235. 1927 Billwiller, John, Method of loosening vegetable fibers. U. S. pat. 1,649,281 (Nov. 15, 1927); T.S. 87: 238; C.A. 22: 500. Ekstrom, P. G , and Hult, R H., Process for the manufacture of sulphite pulp from wood or other fibrous materials. Swed pat. 68,741 (Sept. 26. 1927); T.S. 91: 275. 1929 Michael, Wilhelm, and Palm, Albert, Recovery of sulphite waste liquor for re-use. U S pat. 1,723,800 (Aug. 6, 1929): Can. pat 283,415 (Sept. 18, 1929), T.S. 89: 92; 91: 207; 92:31; C.A 22:4246. Richter, George, A, Recovery of valuable products from spent sulphite liquors U. S. pat. 1,710.272 (April 23, 1929); T.S. 90:204, C.A 23: 2780. Sido, Otto, and Wiederhold, Hermann. Process for the production of cellulose Ger. pat. 505,589 (Aug. 18, 1929); TS 93: 174, C.A. 25: 593 1930 Baker, Webster E. B., Sulphite wood pulp and method of making the same. U. S pat. 1,773,419 (Aug. 19, 1930); C.A. 24: 5158. Richter, George A., Production of sulphite pulp. U. S. pat. 1,780,842 (Nov. 4, 1930); Can. pat. 283,024 (Sept. 4, 1928); T.S. 89: 81; 92: 292; C.A. 25: 206. 1931 Benson, Henry, K., Process for making sulphite pulp from Douglas-fir and other resinous conifiers. U. S. pat. 1,805799 (May 19, 1931); C.A. 25: 3825; T.S. 94: 126. Hixon, Ralph M., Peterson, Charles J., and Werkman, Charles H., Process of pulping plant tissues by means of a U. S. pat. 1,802,715 (April 28, 1931); T.volatile base S. 94: 123; C A. 25: 3836. Richter, George A., Process for the production of chemical wood pulp. U. S. pat. 1,817,525 (Aug. 4, 1931); Can. pat. 309,867 (March 31, 1931); TS. 93: 170; 94:139; C.A. 25:5560 1932 Richardson, Roger W., Pulping process. U. S. pat. 1,885.764 (Nov. 1, 1932), Can. pat. 335,222 (Aug. 29, 1933); ' S 97: 233; 98: 198; C.A. 27: 5538. Richardson, Roger W.. and Sherman, Clarence S., Production of cellulose pulps. U. S. pat 1,851,522 (March 29, 1932), Can pat. 328,828 (Dec 27, 1932); T.S. 95: 204; 97: 318; C.A. 26: 3112. Seaman, Stewart E., Process of producing cellulose. U. S. pat. 1,891,337 (Dec. 20, 1932); Can. pat. 326,709 (Oct. 11, 1932); ''.S. 97: 234, 295; C.A. 27: 2032 1933 Bori, Antonio B., and Estape, Jose M., Process of preparing cellulose. U. S. pat. 1,920,239 (Aug 1, 1933); T.S. 98: 232; C.A. 27:4926. Hahn, Frederick C., and Fothergill, Robert E., Manufacture of wood pulp. U. S. pat 1,926.002 (Sept 5, 1933); 7' S. 98: 198, C A. 27: 5538 1934 Estape, Jose M., Production of alpha-cellulose. Fr. pat. 759,690 (Feb. 7, 1934); T.S. 99: 332. Richardson, Roger W'., Recovery of ammonia from cook liquor. U. S pat. 1,943,345 (Jan. 16, 1934); Can. pat. 353,924 (Nov. 5, 1935); T.S 99: 164; 103: 248; C.A. 30: 1561. 1935 Brill, John L, Ammonia recovery. IJ. S. pat. 2,014,374 (Sept. 17, 1935); C.A. 29. 7597. Kuwahata, Seiji, Pulp for rayon. Jap. pat. 11,240 (April 6, 1935); C.A. 29: 8330; T.S. 103: 70. 1936 Norsk Hydro-Elektrisk Kvaelstofaktieselskab, Recovery of sulphur dioxide and ammonia from sulphite waste liquors. Nor. pat 59,627 (May 6, 1936); Swed. pat. 92,828 (Oct. 11, 1937); C.A. 33: 1938. 181 A
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142
143.
1950 Jesseph, Donald C., Stable bituminous emulsion and preparation thereof. U. S. pat. 2,494,708 (issued Jan. 17, 1950). 4claims. C.A.44:3706; B.I.P.C.20:768. 1951 Parrett, Arthur, N., Wood pulp digestion. U. S. pat 2,564,028. Filed Jan. 17, 1946. Issued Aug. 14, 1951 3 claims. Assigned to Rayonier, Inc., (Cl. 92-11); B.I P.C. 22: 87. 1952 Andersen, Carl C., Treatment of waste sulphite liquor Can. pat. 481,243. Filed Aug. 21, 1939. Issued Feb. 19, 1952. 2 claims. Assigned to Norsk Hydro-Elecktrisk Kvaelstofaktieselskab; B.I.P.C. 22: 643. Helleur, Donald, Treatment of the spent cooking liquor of an ammonia-base sulphite pulping process. U. S. pat 2,596,241. Filed Dec. 20, 1948. Issued May 13, 1952 4 claims. Assigned to Price Brothers & Co., Ltd. (Cl 23-129); B.I.P.C. 22: 799.
144.
145.
146.
MacLaurin
(A Literature Study) Much has been said and many claims have been made with regard to the use of ammonia as a desirable base in pulping operations. To see if these
claims are substantiated and to look a little more closely into the subject this study was undertaken with the following objectives in mind: (i) to collect experimental data on ammonia and its salts, which might have a bearing on the subject, and to do so under more or less specific property headings with the emphasis on base comparisons (Ca, Mg, Na & NHl),
(ii) to relate these properties or characteristics of these bases, ammonia in particular, to general pulping phenomena, e.g., penetration, delignification, etc., (iii) to summarize the experimental evidence in such a way that the pros and
cons bearing on the proposition "that ammonia is the desirable base in the pulping of fibrous raw materials," can be easily evaluated, (iv) to indicate in general terms further possible avenues of research which
might bring out more forcibly the potentialities of ammonia as a pulping base A classification of the ammonia-base pulping literature has already been done; it will serve as a basis and background for the present study.
FORM 73
work, will classify pertinent data from any field and on occasions will review the material critically. The reference numbers of the former work
will be retained in this study; additional references will be renumbered from 1 and followed by the letter A.
Physio-Chemical Considerations (Base comparison) Ion Mobility-Diffusion Rates in Wood In simple aqueous solution (18C.) the ratios of the diffusion coefficients of the chlorides of (taking Mg as unity) Mg, Ca, Na, K, NH, are respectively (19)
1:1,07:1.30:1,61:1.59
On this basis, the .TH 4 ion (together with the chloride ion) diffuses 60% faster than Mg ion and 23% faster than the Na ion.
In terms of the relative rates of diffusion into wood saturated with water, according to the work done by Christensen (19), the NH. shows up even more favorably. ion
to be noted that the ammonium ion shows up best in wood which is normally more difficult to penetrate. In the spotted gum, for example, the NHUl ion
It is of interest to note that the above order of ionic mobility and their diffusion rates in wood follow closely that of ionic hydration and also that of the lyotropic series. The latter series is as follows:
Ca
< Mg
<
In the above comparison in aqueous solution, K and NI-were very close;here, however, (Table I) in the spotted gum (tangential),--for example, the NH4 ion--is 25% faster. Christensen offers an explanation for such ion is weakly basic
it tends to lower the pH, and this in turn represses the dissociation of the -CaOH groups along the capillary walls (IA) and so reduce the resistance to the diffusing anions, which, of course, must accompany the cations to preserve the electro-neutrality of the solution. The discrepancy between
the divalent and univalent ions (especially in view of the hypothesis that the wood is a negatively charged semi-permeable medium (IA) and the bivalents contain a double positive charge) is explained on the basis of the fact that to move through the capillary each divalent ion must be accompanied by 2 Cl ions, and in terms of an activation concept, two Cl ions would have
to possess either simultaneously or in a short period a minimum activation energy before diffusion of the salt as a whole could occur, an occurrence of lower probability. The above work with wood was done with a common univalent anion, while many of the pulping anions are bivalent, e.g., SO 3 , S in Na 2 SO 3
and (NH4)2SO3 , etc., and according to Christensen (19) a bivalent ion (viz., S04 ) has a much lower diffusion coefficient than a univalent ion. Thus while the same general order between the cations (on a univalent basis) would exist on a bivalent basis, there would seem to be a high probability
AND DIVALENT CHLORIDES IN EACH SPECIES AND GRAIN DIRECTION Species Chloride Grain Direction Tangential Radial Longitudinal
Messonate
stringy bark
MgCl2
CaC12
0.53
0.68
NaCl
HC1
5.3
7.8
NH 4 C1 Mountain Ash MgC1 CaC12 NaCl HC1 NH 4 C1 MgC12 CaC1 2 NaCl HC1 TNHIC1 M .Cl CaC12 NaC1 HCl NH 4 C1
9.5 4.45 6.0 15.1 19.4 21.4 0.128 0.185 1.28 1.59 1.99 -11.6 25.3 30.8 29.5 4.0
119 148 470 601 700 2.45 2.98 15.5 17.2 20.3 321 413 707 938 1037
4.95
16.2 20.1 23.1 1 31 1.54 4.23 6.30 7.41 53 51 84.6 93.8 93.2
Spotted Gum
Ioop Pine
within the capillary arising from the dissociation of the carboxyl groups), a reduction in the diffusion rate for a divalent ion could arise out of the lower probability of any anion having the necessary higher activation
energy to overcome this restriction (lower, that is, than the probability of two single anions having the necessary energy). The repression of the
dissociation of the -COOH group by the NH 4 ion would thereby tend to accentuate the diffusion rate differences between the bases. These differences discussed above (ionic mobility and diffusion rates in wood) together with the hypothwsis advanced to explain them have, it is felt, a significant bearing on initial pulping phenomena (e.g., penetration). While ionic diffusion was the particular type of diffusion under review in the above, it might under this topic to note when gaseous ammonia
or solutions contain free ammonia are involved, that diffusion in the gaseous phase is also of interest in base comparison. In this case, ammonia in
relation to the other base (Ca, Mg and Na) is unique; not only can it exist readily in the gaseous phase but it is also extremely soluble in water; in relation to sulphur dioxide, it has a diffusion constant twice that of S02 (0.23 vs. 0.11 cm2 /sec.) and is ten times more soluble in water (24A).
2/sec. The diffusion rate of water vapor in air is approximately 0.22 cm
1516
May 13,
Vapor Pressures--(aqueous solutions)
1954
The partial vapor pressures of ammonia in aqueous solution (i.e. ammonium hydroxide) is quite high even at low concentration gives some data in ranges of interest in pulping.
Table II (3A)
partial pressures of the other bases (Ca, Mg and Na in hydroxide form) is substantial zero; and this, of course, is true of any of the salts of these bases in aqueous solutions. When one examines solutions of the salts of ammonia, the partial pressures, while much reduced, are often quite significant pressures vary with pH, temperature and concentration. These partial
In the case of
ammonium sulphite in aqueous solution above the pH of 7, where the normal salt ((Na 4 )2 SO3 ) exists, the partial pressure is substantial at concentration in the pulping range, as the pH drops below 7, the concentration of the acid salt (NM4HS0 3 ) increases and the partial pressure falls, but at elevated temperatures it For example, is quite significant even for low concentrations. NHi , at 160.C. 3
and pH of 6.0--the partial pressure of the ammonia is 104 rmm. and that of the sulphur dioxide 128 mm.; in contrast, that for the sodium salt at equivalent concentration and temperature, the v.p. of Na = 0, and that of
the potential of ammonia as a driving force is 100 times that of Na, and the S02 2.8 times that of the S02 when associated with NaOH. This situation is
much the same for other salts of ammonia especiall those salts of weak acids),
e.g., ammonium sulphide (i.e,, the hydrosulphide), ammonium carbonated
TABLE II PARTIAL VAPOR PRESSURE FOR SYSTEM: NH 3 + H20 ( p m ' (From Volume III, p. 362, Int. Crit. Tables (1928))
+C.
20
Mol % IH 3
5
51.7
10
15
142.9
20
+C.
Mol %
5
2386
10
15 4724
6028
20
87.8
224.7
120
3457
6337
8000
40
131.8
316.5
22r5 517.2
353.5
772.5 1,527
2,777
543.0
1,123.5
3129
4465
5683 7142
8381 10920
60
80 100 110
4042
5151
6L87
7592 9446
9978
2,154
3,814 4,953
3,671
8073
PrOject 1516
Page 8
above)
on numerous physical-chemical properties of solutions has long been known. Stamm (2A) has shown that saturated solutions of salts caused a swelling of wood at room temperature beyond the normal water-swollen state and that the order of swelling was roughly that of the lyotropic series. summarizes some of the data. Table III
the NH4 and Na ions were the least affected in swelling of wood, and their effects were the same on a chemical equivalent basis Ca and Mg were similar
in their effects, and on an equivalent basis, assuming a proportionate decrease in swelling with a decrease in concentration (2A, Fig. 2, 1198), Ca and Mg were approximately five times more effective than Na and NH3 . However, in terms of lower concentrates (molar e.g) while the differences
may remain of the order of five times, the absolute values are comparatively small (0.1 to 0,02%). The time factor also tends to nullify these differences
between the cations where judged in terms of pulping periods; for example,
Stamm (2A) noted that while swelling with most salts was complete in a few days, Ca and Mg required a week to come to equilibrium, In times of other
salts, e.g., sulphites and sulphides, presumably the order and the differences between the cations will remain.
TABLE III Molar Concentrate 20C.per Kg solvent 13.4 11.5 6.1 6.9 Swelling of wood beyond water-swollen state Tangential % Radial % Volumetric 1.41 0.90 .12 .12 .26 1.75 1.11 .12 .12
.13
.00 .00
Project No. 1516 Page 9 May 13, 1954 Stamm's (2A) study also indicated that the effect of pH on swelling was negligible below a pH of 10; above 12 the swelling increased rapidly; at 14 it was 2.5% beyond that of the water-swollen state
0
On this basis,
the pH attainable by the various bases becomes significant (see"pH'" below). Welting Property-Surface Tension Data is lacking for the salts of interest.
However, a guide to
the direction in which the surface tension (gas-liquid interface) of aqueous solution of the salts of the bases might lie is again given by the lyotropic series (see"Immobility" above); thus those cations at the Ni and Ba end
of the series give surface tensions having a smaller increase above that for pure water. For example, at 20Co, and 1.0 mols per Kg solvent the surface
tension (A) (air-water solution interface) for NH 4 Cl, NaCl, MgC12, and CaC12 are respectively 1.4, 1.6, 3.0, and 3.2 dynes per cm. above that for water at 20C.(72.8). and sulphides. results, Presumably such a trend would hold for the sulphites, bisulphites In the case of the hydroxides, ammonia apparently gives even lower NH4LOH (1.5 mols Kg
solvent at 20C.) are respectively 75.9, 75.7, being actually lower than that of water(72.8). Emulsification, dispersion, peptization
There seems to be very little data of work done on the peptizing effect of the various pulping liquors on the various components of the wood;
sometimes indirect reference is is built around it, but little made to this property (10), direct evidence is given. on a hypothesis
In general, we know that alkalies are often good emulsifying agents.In certain applications, where various substances are being peptized, it has been found that the peptizing effect of aqueous ammonia has been out of proportion to the [OH], the implication being that the ammonia is exerting a specific effect (4X). In this regard, we know that adsorbed substances
will tend to peptize the adsorbent and that the NH4 ion has a fairly high adsorption tendency (5A). Also the ammonia, having a tendency to form complexes,
might bring about peptization through the formation of organic colloidal complexes sooner than if this tendency were absent.
Examples of commercial applications where apparent advantages are attributed to this property of ammonium salts are: ammonium sulphite is
considered a good solubilizer for shellac (6A); ammonium salts of casein (7A), of sulpho compounds, e.g., th 4 salt of butylated naphthalene sulfonic In fact, N-compounds usually containing
acid, are considered good emulsifiers. the NTI3 or the NII 2 group,
On the other side of the picture, salts exert a lesser peptizing effect.
that is
saturated solution of the salts of various bases cause a peptization or partial solution of cellulose (at temperatures above 135C.) in the order of the lyotropic series; in this particular case, ammonia is scale; the best place to be. at the low end of the
Coagulation A property similar to the above in in pulping phenoona but pposite in result, relation to desirable effects is coagulation or the salting
relative position of the cations with respect to their ability to coagulate, and NiH least.
3
is again at that end of scale where coalutlations effects are the The mechanism of coagulation is usually bound up with the hydration and so we find that the coagulation order of the cations
of the ions,
various superimposed solutions of electrolytes may be important to the mechanisms of penetration and pulping; condensation or coagulation of these sols could easily influence the flow of materials in and out of the finer capillaries.
There seems little doubt that of the four main pulping bases (Ca, Mg, Na capacity and IH ) the ammonia salts exhibit the greatest buffering This is espe cially true of the actual pulping salts, the
sulphites, etc., as they are salts from both a weak base and a weak acid; and for this reason, we find that the differences in relative buffering capacity is greatest on the alkaline side, and least on the acid side (the weak acid being a common constituents.
In terms of actual pH, on a chemically equivalent basis, the ammonium salts tend to give a lower pH on the alkaline side (i.e., to pH7); for example, close
pH of 9.8, while at the same concentration, an ammonium sulphite solution would have a pH of 80 On the acid side differences are slight and in the bisulfite
range the tendency is towards a lower pH for the ammonium salts. Comparison of the attainable pH of the hydroxides of Na and NH3 bring out one of the largest drawbacks of ammonia when considered in relation to present "alkaline" pulping conditions (kraft and soda pulping). For example,
on a tenth normal solution basis the pH of ammonia is ll.l and of NaOH 13.0; higher concentration would change the pH very little, the spread between the two if anything would increase This difference of "attainable pH range" is
apparently important in the mechanism of delignification and penetration of "alkaline":pulping; swelling, for example, is affected (see above). Viscosity Table IV gives the viscosities of a few aqueous solutions of the salts of Ca, Mg, Ha and H\14; water is the reference material. As shown in the table, the ammonium solutions have the lowest viscosity; MgSO; in comparison with (NH )SO 3 is approximately 30% higher in viscosity. TABLE IV (Values referred to water (O1A)) Ref. Temp.-25C; concentration-1 mol. per 1000 g. water for the univalent compds. 0.5 mols per 1000 g. water for the divalent compds. Salt CaC12 Ca(N0 3 ) 2 MgC12 Mg(N03 ) 2 MgSO 4 Viscosity 1.15 1,12 1.20 1.17 1.37 Salt NaCl NaNO Na 2 S84 (0.5) NH4C1 2 NH4 NO 3
(hH 4 ) 2S0/
4 (0.5)
V iscosity 1.10
1.06
1.23
0.991
0.96 1.05
Osmotic Pressure
Of the very small amount of data available on the osmotic pressure of aqueous solution of various salts, indicate that ammonium salt solutions probably give osmotic pressures higher than those of other bases (Na, Ca and Mg). For example, (using a Ca ferrocyanide membrane) the osmotic pressure for 11N O, 3 NaNO3 , K2SO4 and (NH)
2 S04
for a concentration of 25 mols per 1000 grams of water at 15C. (3A) ; this would put NH4,ahead of K and Nai&with the lyotropic series as a guide (see "Ion mobility" above) the inference would be that Mg and Ca have still lower pressures (on a chemically equivalent basis); such a situation holds true when Ca and Mg are compared with Na and K or a ferro- and ferricyanide solution basis (2A).
The significance of these pressures on pulping might be that solutions with higher pressures would tend to rupture intercellar membranes, etCo, quicker and thereby increase rates of penetration and delignificatio..
base pulping liquors give somewhat higher concentrations of free S02 at a given equilibrium pressure than does a line-base acid. For example, at approximately
2% combined SO2 (at a given pressure) the total SO2 in an NH3 -base liquor would be 8% while in an Ca-base liquor it would be approximately 75%[(54)-Fig.5) it is thought that the explanation for the difference lies in the different degrees of ionization of the two bisulfite salts. for the other bases Na and MgO. No data has been published
(56% CaO and 40% MgO) and pure lime, however, show no significant difference, indicating that the solubility relationship for the MgO is substantially the same as for CaO. Degree of ionization considerations indicate that
possibly NH4 base liquors would also give higher SO2 concentration than Na-base liquor.
A few miscellaneous chemical or psuedo-chemical reactions are listed to exemplify some specification which is apparently attributed to the ammonia. (i) Calhoun & Maass (llA) investigated the effect of pretreating wood in aqueous salt solution on subsequent delignification in sulphite liquor. Table V summarizes some of the results. As the pH of the pretreating liquors
in each case within the range (4-6) which Corey & Maass (12A) have shown to have a minimum effect on pretreatment, differences in [H ] can be ignored. Examination of Table V indicates that the sulphur content of the liquor varies inversely as the lignin content of the pulps; Ccrey & Maass deduced from this
that pretreatments probably hinder sulphonation more than it does the hydrolysis of the sulphonated lignin. Hindrance of this sulphonation seems a straightfor-
ward pbservation, but since hydrolysis would seem to depend on sulphonation as a first step, judgment on which reaction might be favored would seem to be less straightforward, Comparing the various cations with each other and with
the lyotropic series, indicated that the alkaline earth metals are in the reverse order and the alkali metals in the same order as the serie. however, was found to Ammonia,
Project Nc. 1516 Page 15 May 13, 1954 TABLE V EFFECT OF CATIONS IN PRETREATMENT Pretreatment: 6 hr. at 140C; cooking 3 hr. 1400C Pretreating Soln. 1.0 mol Pulp Yield % Carbohydrate Yield, % Lignin as % of Original Wood Sulphur as of Lignin
NH4 N03
67.2
43.6
23.6
3.47
HC1
58.6
47.3
11.2
5.98
(ii) Cross (22) in his work using very low concentrations of ammonium bisulphite to pulp spruce wood felt that ammonia exerted a specific action on the lignin. (iii) In the reaction of styrene with bisulfite (13A)
PhCH2 CH2 S03H(A) + PhCH.CHSO3H(B) + 2-hydroxy-
2-phenyl ethanesulfonic/Salts
(B) at the expense of (A) morw than do the alkali metals (iv) A study of the Willgerod reaction (14A) involving olefins,
tertiary carbinols) indicated that NH 4 CH4 salts (e.g., (N'H 4 )2 SC) seemed to
have a specific effect on product yields. (v) Ammonium salts appear to repress resinification occurring between sugar and animal glues (15A). (vi) Hemolytic action of ammonium salts--corpuscles relatively impermeable to ammonium as well as other cations, will let anions like Clland OH as well as NH3 molecules pass freely (16A).
(vii) Ammonium salts of inorganic salts (as well as stronger organic acids) increase the activity of ptyalin (17A).
Allied Reactions
A few reactions that might possibly have a bearing on the chemistry of ammonia-base pulping are listed.
(i) Japanese workers (18i) heated hexoses with ammonium salts OH^. OH HO/ H OH -,H A at 150-160Co to get f
(iii)
were obtained by Egli (a2A). (iv) A patent (21A) was taken out for the production of any
Catalytic Action This consideration probably overlaps that of "specific action;" however, since one comes across the term in pulping literature it is treated separately. Evidence of any catalysis which might be attributed to the
ammonia, the ammonium ion or other derived compounds is very sketchy and not specific or definite to relation to pulping reactions.
To organic chemistry, ammonia and ammonium salts are generally considered good catalysts, especially im ammonolysis (22A); also in condensation
Project No. 1516 Page 17 May 13, 1954 of phenols with CH20 (23A); preparation of proponic acid from ethylene (23A); and converting acetic acid to metaldehyde, etc. Vague references, in the field of pulpingare made to the possibility of a catalytic reaction involving ammonia. For example, Cross (34)
(22) attributed the faster or more efficient pulping actions of ammonium bisulfite to a catalytic effect of ammonia, Such claims, however, although not
PULPING PROCESSES Penetration Penetration in one form or another takes place throughout the whole pulping cycle, so to study the factors involved other than delignification and to make comparisons between various pulping liquors, one is confined to the period prior to where the delignification process becomes prominent, as, at that time, it itself becomes the controlling factor in penetration phenomenal It is this prior period or initial penetration with which we are concerned here. A recent comprehensive treatment of "penetration" (and diffusion) is given by Stamm (24A); while it is somewhat bibliographic in nature, his summaries and included data make it good background material 0 In his intro-
duction he states "The mechanism of the movement of liquid as well as of gases, vapors, and dissolved materials into or through wood is still not thoroughly understood, however, in spite of the considerable research that has been carried out on this subject"
Project No. 1516 Page 18 May 13, 1954 A. There would appear to be at least four distinct steps involved
in penetration: (i) wetting of the wood surfaces by the solution (or condensation), (ii) diffusion of water vapor into the capillary structure, (iii) capillary rise of the solution into this structure, and (iv) diffusion of the solution into the cell walls While the steps would take place
in the order given, (i) may be considered as a preliminary rather than primary step, so that the rate at which (ii) takes place becomes the controlling rate of absorption of the cooking liquors (24A)(25A). Stamm in his earlier work (25A) concluded that
(i)
Rate of Wetting.
wetting agents (i..., depression of surface tensions) were of no practical importance in increasing the rate of penetration His conclusion was based
largely on the following facts, (a) the increased water take-up due to wetting effects was a small fraction of the saturation value, (b) the decreased time involved was a very small fraction of the total time (96 hr.) (c) the lower surface tensions resulted in lower capillary forces (which were at that time considered the controlling factor) which tended to cancel out any gains due to setting He noted nevertheless that in the first few
minutes wetting did increase the rate of adsorption substantially within that period; this, however, was only true for floating wood and not for submerged wood. In partial disagreement with his final conclusion (above),
it is felt that liquors with low surface tensions would be of practical importance in promoting penetration whenever short penetration periods and lower water to wood ratios are involved; especially when corresponding lower
Project No. 1516 Page 19 May 13, 1954 liquor viscosities are present to compensate for the lower surface tension. On this basis, examination of the data under "surface tension" and "viscosity" above, indicate that in respect to rate of wetting, NH 4 -base liquors would be the most effective. (ii) Rate of water vapor diffusion. On first thought this factor would
appear to be of no significance in base comparisons of pulping liquors.However, in cases where free ammonia is present, the slightly higher diffusion rate of ammonia gas (see the end of the section of "Diffusion"--above) and its great affinity for water could conceivably bring about an increase in the rate of water vapor diffusion over that where other bases were used.This high diffusion rate for ammonia would also in certain cases prevent chip burning from taking place.Use of these properties of ammonia gas is made in a wood pretreatment process to simulate air evacuation of the chips (24A) (iii) Rate of capillary rise. The relationship between capillary rise
and other physical properties is given by the following formula (25A): h + -where h = ht of capillary rise in time t of a liquid with surface that completely wets the fibres, and r is the radius
"Surface tension" above show that the lower viscosities of ammonium salts solutions more than compensate for the lower surface tensions; the expected
trend, therefore, is for the pulping liquor of ammonia base to be made effective in terms of capillarity than those of other bases. Rate of diffusion into cell walls--The factors that have already been discussed in the above (i, II and iii) such as vapor diffusion, viscosity,
are also operative here, so on that basis of comparison, NH4-base liquors would tend to be more effective than other base-liquors in promoting this aspect of cellwall diffusion. Be Other Factors Involved in (ii)(iii) & (iv) While only the more or less direct or obvious factors have been consideres in the treatments of the various types of "rates" involved in penetration, there are many other considerations which influence these "rates." They will be considered in conjunction with physio-chemical factors set out in the previous section. (a) Swelling. The influence of the swelling of wood on the rates of On a causal basis, swelling might be considered
to be two types, that which is the result of the physical absorption of water, independent of the influence of any other chemicals present, and that where the water absorption is influenced by the presence of chemicals.It is the latter type of swelling with which we are mainly concerned. Data on "swelling?"
in the previous section show that below a pH of 12, neither pH nor the specific effect oflthe various cations is of much significance; over a pH of 12, the controlling factor is pH so that swelling effects are reserved for those cations (bases) which are of themselves capable of promoting high [OH] concentrations. MgO & CaO are ruled out, because their low solubility make them impractical
pulping chemicals in the alkaline field, ammonia is ruled out because the pH of its solutions do not go above pH 12, this leaves Na-base a unique base in the highly alkaline field,
involved become very difficult and in a sense of little practical significance. However, of the factors involved, swelling would appear to play no
small part, in spite of the fact that since this swelling is internal, first thoughts are that this internal swelling would tend to close off or decrease the size of the capillaries and so decrease penetration. Swelling,
however, seems to influence structures other than the gross capillaries so that the overall effect is large increase in penetration; the concept that swelling of the cell wall takes place opening up the pores (pits) within the walls allowing for rapid transient penetration is one such example. (b) Peptization. A phenomena which has not as yet been given much
prominence in penetration studies, is that of the peptization, or in a broader sense, the dispersion., molecular or colloidal, of the various wood components (other than lignin and cellulose) by the various pulping liquors. It would seem that peptization of some extraneous wood components, e.g., resins, gums, etc., leaving the wood more permeable to liquids and chemicals, could go far in explaining penetration phenomenal Many of the pores (pits) of the
cell walls are ineffective because they are frequently sealed with resin; this is also true of many of the capillaries, especially of such species as the pines, spruces and Douglas fir (24A). Pretreatment work (10)(59) on
Douglas fir with aqueous solution of ammonia is also evidence of the importance of this factor. Strong alkalies are generally good peptizing agents.
so that it
under very alkaline conditions are attributable in no small part to the peptizing action of the caustic . In the acid and lower alkaline ranges,
specific cation ion might possibly play a part; what little evidence there is of the comparative position of the bases indicates that the ammonia and
its salts would be the more effective than any one of the ther bases, in
promoting peptization. (c) Coagulation. What part, if any, coagulation effects might play in
penetration would be difficult to evaluate; although it is not inconceivable that many of the biocolloids present in wood are sensitive to coagulation by the various cations. At any rate, it would appear that if such effects are Example (V)
of "Specific ActiorAbove might be of some significance in this respect. (d) Osmotic Pressure. Rupture of intercellar membranes by osmotic pressures is Its possible
influence, like coagulation, is obscure; the possibility remains, however, that if operative, ammonia and its salts would probably be more effective than anyone of the other bases in promoting this aspect of penetration. C. Other Considerations (a) Vapor pressure Gradients. While NaOH is unique among the four bases
for its high pH and solubility, ammonia is unique for its high volatility and solubility; so that in terms of base penetration under very alkaline conditions. ammonia because of its high vapor pressure, compares very favorably with NaOH
falls down in over-all results, for while the ammonia itself penetrates rapidly, secondary effects, swelling, etc., do not take place to aid in the bulk penetration of the pulping liquors However, for penetration under less alkaline
or acid conditions, we find that ammonia and its salts lead the field (see "Vapor pressures" in previous section), as not only do high vapor pressure
of the base prevail, but those of the acidic constituent (e.g., S02) do also; this means that the pulping chemicals come into contact with the wood sooner when ammonia-base liquors are used This is important where "burning" of the
wood by wood acids is to be avoided when using minimum periods of penetration. It is probably in this latter field of "short periods of impregnation" that the value of ammonia lies. Actual laboratory confirmation of this is made in Here the chips were pretreated with
ammonia and then cooked with free S02 liquor, and the penetration period practically eliminated, so that the
FIT 3
was followed with preheated S02 solution at the maximum cooking temperature; results were very satisfactory. Another very interesting result in this second
series, adding NIa 3 and SO2 in gaseous borm, was that Bryde was able to pulp pine heartwood very satisfactorily; pine normally is very difficult to pulp with the usual Ca-base sulphite technique. (24A). Stamm also speaks highly of this aspect
Certainly many patents have been taken out with this feature in mind,
e...,
(116)(121)(140).
(b)
when the wood has become more or less saturated with liquid,
the rates of diffusion of the dissolved materal become an importart factor in penetration. While on the one hand, these diffusion rates are dependent they are also dependent on This former con-
sideration has already been discussed in the above whenever such factors as capillarity and cell wall pore size were involved. In the case of the latter
consideration of ionic mobility, examination of the evidence presented under "ion-mobility and diffusion rates in wood" of the previous section indicates that ammonia and its salts are more efficient than anyone of the other bases in promoting rapid diffusion of chemicals into the woods.
Delignification (de-hemi-cellulosification,
etc.)
While many careful more or less fundamental studies have been made of delignification, few have been made with a base comparison the i The of
Acid Sulphite.
While few fundamental base comparison studies have been made Many of these indicate that obtained when
or no gain in yield or quality of the final product is substituted for another; for example, Aronovsky (on straw)(7), no difference if
one base is
Hagglund (32),
the cooking is
bleaching requirements.
While these results indicate what one might expect under a set of conditions comparable to commercial Ca-base pulping, they tell little of the hidden potentialities of the various bases.For example, let us assume that Ca is by far the least promising of the four bases. This means, to produce a "satisfactory" Ca-base pulp, the process must allow for all the inherent drawbacks of the base, e.g., poor penetration, with the result that long penetration periods and comparatively gentle pulping conditions are used; in addition an "acceptable" has for a long lime meant a pulp, low in yield and correspondingly high in the "resistant" cellulosic fraction, "resistant," that is, to the point that any undesirable or desirable features of the base would not show up. And it is under these sort of conditions that
the work, reported by the above authors, has been done, and the results evaluated in terms of this insensitive low yield cellulosic fraction results say nothing about whether one basis penetrates the wood faster than anotner so as to indicate that the long penetration periods were unnecessary; certainly the low yields at which comparisons were made would not indicate this, as penetration periods twice as long could hardly have made the yields any more lower, and this is true also of such factors as comparative rates of delignification, selective degradation of hemi-celluloses, etc. The
9A (A)9A)(A)
Only (95) treats of bases (Ca, Mg, Na) on a comparative basis; the other references are listed for general references Yorston, in his "studies in sulphite pulping"
reports on "The Effects of the Base on the Yield of Pulp" and "---on the rate of delignification"; unfortunately, [H 3 was not one of the bases studied. The
at 05% combined and 90% delignification Na-base cooks faster than Mg-base and much faster than Ca-base; at 1% combined their rates are about equal; at higher concentration the Na-base is slower; apparently, at concentrations above"2% combined" rate of carbohydrate degradation is independent of the base; at "0.4% combined" rate of carbohydrate degradation is fastest for Ka-base and slowest for Ca-base. To the case of a wood species like Jack pine, the heartwoods is
extremely resistant to Ca-base liquor but is more completely attacked by the Na-base liquors. However, since only a small part of this general study was
concerned with more or less fundamental aspects of base comparison, many angles and questions remain unexplored In terms of ammonia base, it is expected that
one of the bases (although less fundamental than the above work) are:
H-i4-base
in contrast to other bases gave a higher rate of sulphoration (58); evidence that NH4 -base gives a higher yield of a-cellulose (and consequently a higher yield of pulp) than other bases, the a-cellulose content was lower, however, than the Ca and Mg pulps since in the latter one liquor and pentosans are removed (1b)(59), 1,H-base liquor dissolves more lignin in preference to cellulose (4)(38). Engelstads results (34)(28) indicate a difference of several % on
Page 13, 1954 a "% screenings basis (at equivalent unscreened yields--50%)with ammonia-base giving the least screenings of the four bases used; according to Cross and Englestad (22) use of Ti' 3 (in contrast to the other bases) makes the pulp more
susceptible to overbleaching (i.e., production of oxycellulose). Results where NH was the sole base used are difficult to interpret
in terms of possible base preference as often the species was one on which little, if any, fundamental work was done, or the conditions are the conditions sufficiently different to make comparisons hazardous, e.g., Benson's work on Douglas fir (11). Neutral Sulphite. Few results on base comparisons (NH 4 and Na) have been re-
ported in this field; Boot and Herschel (15) report of their work with straw, they found little difference between Na and NH4 ; their study was, however, very brief. A good study on white fir using NH 4 -base alone is (36); work done at
the Institute of Paper Chemistry can be found under project 1516. .Tne impression obtained from the above reports and any work done by the author is that the differences found between the bases under acid conditions are somewhat magnified under more alkaline conditions, i.e., the NH4-base liquor attack the hemi-cellulose less aggressively than do the other bases, and if anything, the lignin is attacked more strongly. The net effect
is that NH-base neutral sulphite pulps give higher yields of screened pulp
for a given screening fraction, the pulps themselves are somewhat slimy,
"hydrate" rapidly in the beater and give fairly high strength values, comparable at times with kraft values.
Alkaline process
The term "alkaline" is usually associated with pulping with the hydroxide or the hydroxide and the sulphide. While some work has been re-
ported on pulping with NH4 OH, little, if any, has been made on work done using NHO 4 0H and (114)2So Some work, however, has been done at the Institute 992-1).
For articles dealing with cooking with using NHIOH, reference should be made to the literature classification of Section I of this survey.
In the case of pulping with NH4OH, the general conclusion at present seems to be that in comparison with NaOH, NiH4OH is far from being a useful and satisfactory pulping agent residues (7). This is true both for wood and agricultural
of a good pulping liquor, it is not able to provide a sufficiently high enough pH (i.e.[OH]) to bring about rapid dissolution of the lignin. of pulping with NH4 0H and (H to be noted, however,
2S 4)
And in
the case It is
very meagre;
much work could be done before it are not practical pulping liquors
can be said conclusively that these liquors For example, an apparently unimportant
change in pulping conditions leading to more satisfactory results can be found in the Institute project 992-1, where pulping was done with 0'HOH and elemental
sulphur. Here by increasing the degree of agitation of the wood charge and liquor a fairly satisfactory pulp was obtained.
General Discussion As has already been stated, the impression (plus evidence) in some quarters is that during delignification, etc., the IlL-base pulp will liquor
seems to attack or degrade the hemicellulose (% cellulosic) fraction of the wood less than do other bases, with result that the higher yield NH4(pentosans). Is this desirable?
most cases, an exception being where a high a-cellulose pulp is desired as in particular types of dissolving pulps. For example, according to
Tonas & Rieth (31A) "it cannot be doubted that the preservation of the accompanying carbohydrates which increase the strength, may be striven for as much as possible through suitable choices of cooking condition, when materials with good strength properties have to be produced", their experiments support their premise This view is also supported by Runkel (32A).
Beating time is also decreased with increasing hemi-cellulosic content (32A). Certainly yields will be higher and under conditions of wood scarcity this is an important consideration in itself. In regard to yields, Runkel (32A)
points out that about 25-30,, of the wood can be termed hemi-cellulose and of this 50-75.i is easily hydrol-zable so that this fraction would be the a high yield pulp of low lignin content; the other more
difficultly hydrolyzable portion presumably would be available under most cooking conditions involving any base. Over and above this potential hemi-
cellulose fraction, a gain is to be made on a cellulose basis, since by aiming to retain most of the hemi-celluloses will be degraded a smaller fraction of the cellulose
1516
base in delignification?
As to the latte
question. the various "experts" have given their varied opinions, emphasis seems to run from, its role is
and the
Buffering action.
generally accepted
allowed
to increase would degrade the cellulose and increase the rate of attack on the hemi-cellulosic fraction; however, the buffer action also controls
the [HIS03-] and this to an important extent relates the rate of delignification, i.e., the greater the concentration the higher the rate. However,
somewhat difficult;
one attempts to explain them on the basis of the pH of the original liquor the facts do not add up, as ammnonia-base liquor tend to give (see "Physico-Chemical Consideration above) so one would expect
more degradation;
the [H ] and [HSO 3 ] under actual pulping conditions are It is conceivable, however, that under pulping con-
ditions the [IT ] could be suppressed through formation of NH + complexes having lower degrees of ionization, thereby increasing the [HSO3-2 in attempt to maintain the original degree of ionization its
in obtaining a holocellulose fraction through use of monoethanolamine could be attributable to such a mechanism,
1516
Specific Effect.
The concept that certain bases exert specific Cross (22) supports this (as low as 0.1%
view for 1\I3, with his statement that small amounts of 1Ki
cooking liquor basis) where able "to improve the resolution (i.e., delignification) out of all proportions to its active mass"; otherssupporting this view are Doree & Hall (27) and Hansen (3/)(by implication). mentions it as a possibility in the case of Na-base. Yorston (OA)
tabulation under "Specific Action" page above show, ability to promote specific or catalytic effects.
Further Conjecture. Chemical consideration. Doree & Hall (27) and Doree and Barton
Wright (26) tried to establish the make-up and structure of the ammonium lignin compound; they found that while all the N was recoverable as NH3 on boiling with strong bases (caustic) it was not all recoverable by acidi-
fication (HCl) followed by dialysis; this latter result led them to believe that possibly all the N was not tied up simply as the NH4 ion but that other addition compounds were present, e.r., aldehyde-ammonia, since the sulphonic acid is strongly aldehydric in character. Previous work by the author with by these
ion-exchange resins indicated that some of the NI was unrecoverable methods; this supports the dialysis experiments, although it is
admitted
that other explanations are available to explain their incomplete fractionations. caustic, ion, It would seem, that the fact of recovering N as
3
bH boiling with by
was not necessarily conclusive proof that all the T,exists in the yield H3
Project Page 32
oo. 1516
The possibility that the Ni3 does in fact react in a way radically different from other bases, does not seem to be too difficult a fact to accept in the light of the inherent properties of the nitrogen atom: its ability to change valence easily, to form various types of bonds (e.g., semi-polar double
bonds) which in turn accounts for its ability to form oniun compounds (the amides and amines are a case in point, here the original basic character of ammonia is not lost but is still retained by the compounds it forms).
On this basis, it may be that organic compounds are formed during the cooking
of the wood which are themselves somewhat "basic" and which, therefore, extend the "basic" potential beyond what it might be on the basis of the original ammonia. Physio-Chemical Considerations. However, aside from buffering
and specific or catalytic effects, there are many other considerations to examine. The list of properties (on a cooperative basis) above (see previous Higher ionic mobility and diffusion rates
may help (a) in removing the "destructive" products and so minimize detrimental local conditions; (b) to maintain the buffering capacity of a given base at its optimum level, etc. In fact, most of the physio-chemical properties
such as higher vapor pressures, greater solubility of SO2 in the salts of the wood products, could, by effecting more efficient mass movement or maintaining
an optimum physical structure for rapid delignification, be used to explain base differences. ties, it And since M/i 4 -base leads the field in most of these proper-
(1) There is still a great amount of fundamental research thatcan be done on ammonia-base pulping, especially with base comparisons in mind; it is only by making these base comparisons that one can obtain, the
maximum benefits that may be derived from a choice of any one particular base.
(2) The present evidence points to ammonia as the desirable base under the major of pulping conditions This is summarized in Table V.
The main criteria used in classifying the various properties has generally been that which will promote rapid penetration, rapid delignification (i.e., shortest pulping periods) and decreased degradation of hemi-cellulosic and cellulosic fractions (i.e., give high yield of the cellulosic material of the wood).
(3)
ing effect of ammonia as a base that ammonia does exert a specific or desirable catalytic effect during pulping; this evidence, however, is not conclusive. Ammonia and sodium would appear to behave similarly in many of is the pulping reactions and it/probably between these two bases that any apparent advantages will have to be carefully evaluated (4)
Further Research
The question often is not only where best to begin but also at what level (i.e., "fundamental" pr 'practical"); this question is often a contentious
interested at the moment in finding out "why," "why do these things happen as they do"; those with the more practical bent are primarily interested in finding out "how," "how do we go about getting the desired results now, on a practical scale." The former, of course, are always interested in "how"
but they believe that "why" will allow them to get at "how" more efficiently in the long run, even if they do have to use less practical conditions at
the outset; the latter see little use in hypothetical cases. have a good case. Both it seems
little compromise on the level at which the experimental work is to be done, rather it be done in as fundamental a way as possible or as practical a
way as possible, so that at least each group will be closer to the answer to his particular query; an experiment at a compromise level will probably leave no one very satisfied.
The following list of considerations indicate in very general terms a few of the many interesting angles to explore:
Comparison of the delignification and "de-hemicellulosification" , Ka, Ca and Mg, as well as the effect of the ratio of these rates the , of the original hemicellulose and lignin left on
Probably wood meal would be the best medium to work with; the program
could very well be very similar to take reported by Yorston (2A) in which Na, Ca, IL were compared. While all fields of pulping should be investigated, possibly
2.
This
might rive a lead as to whether or not the main problem in the use of divers species is a problem of adequate liquor penetration.
3.
Determination of the most rapid rise to maximum temperature that the various level.
4.
Determination of the extent to which reuse of pulping liquors It is possible one base may be more
can be made using the various bases. amenable than another to reuse.
traneous wood components, such as the wood resins, could also be studied with an eye to penetration problems, and also in comparison with the data that might be obtained under the example of 6. below.
5.
Determination of the lowest permissible chiemical-wood ratio for be done at a fundamentala" level using wood meal
6.
the various liquors that are used or might be used in actual pulping, at temperature and pressures of practical interest,
mean filling in the gaps of some of the properties listed in this study, e.g. the ability of each of the liquors (for each base) to peptize or dissolve some of the extraneous wood components, such as wood resins; such material could be isolated and treated under controlled conditions,
Project No. 1516 Page 36 May 13, 1954 7. Characterization of each pH range in terms of the pulps that each range produces, especially in terms of pulp strength--this would help to evaluate the importance, if any, of cooking in very alkaline conditions.
ADDITIONAL REFRENCES (1935) J. Phy. Chem, 49:49, 171, 265 J. Amer. Chem. Soc. 56:1195-1202 (1934)
International Critical Tables (1926) Bancroft--"Applied Colloid Chemistry" 1932, p. 209 ibid. p. 207 Paint Tech. 11, 141-2 (1946)
(9A) Herzog & Beck, Z. Physcol. Chem. 111:287-292 (1920) (10A) Int. Crit. Tables, Vol. V, p. 12-15 (1928) (11A) Caihoun & Maass, Cd. J. of Research B. 15:80-83 (1937) (12A) Corey & IIMaass, Cd, J. of Research 3. 13:149-155 (1935) (13A) M. S. Kharasch Remsen Ten Eych Schenck & F. R. Mayo, J. Am. Chem Soc. 61:3092-8 (14A) C. A., Vol. 41, p. 735 (15A) C. A., Vol. 43, p. 6454 (16A) C. A., Vol. 19, p. 1718 (17A) Proc. Am, Soc. Bi.l. Chem,, J. Biochem. 33--IX-X (1918)
Egleff, "Catalysts"
(1940)
A. J.
Diffusion & Penetration Mechanisms of Liquids into Wood, of Canada Feb. 1943, p. 54-63
(25A)
Stanm,
Petering, W. H.
Explained by means of quick cooks--Finnish P. Timber J. 29, no. 296-301, 322-3; no. 21:317 (Oct. 31, IKov 15, 1947)
(Translation in Files). O27A) Beazley, W. B., Campbell, Ao B., Maass, O. "The physical properties of 93 (1938).
Maass,
which Influence Sulphite Cookin'g", Dom For. Service Bull. (29A) Deazley, W. B., Johnson, H. W., Maass, O.
Cooking Liquors and Other Media." (LOA) (31A) Yorston, Lonas, Fo H. "Studies in Domr.
'7 (1935).
For. Ser.
Sulphite Pulping",
Dom. For.
Influence of certain heui-cellulose on the Wochbl. Papierfabr. 64. no. 48:853-5(Dec. 2,1933)
Runkel, Roland. The technical importance of the cellulose accompaniants (i.e., hemicellular). Papier-Fabr. 31, 75-7, 86-9, 97-100(1933)o
Project No.
1516
TABLE VI MIGHT BE THE DESIRABLE PULPING PROCESS IN SUMMARY OF EXPERIMENTS INDICATING THAT Ca, Ilg AND Na WITH COMPARISON See Page 2 Con Undecided Possibly of no Significance
Property or Consideration
l.
2.
Ionic mobility (chlorides aq. soln. at 18C.) Diffusion rates in wood (chlorides at room tempo)
4 fastest in all cases reported; rate varies with species and grain direction; one case 16 times faster than Na which is often a close second All conditions, V.p. of both IN3 & g. 2 (when used) substanhigher. tially pH> 12--NaOH alone in the field
3.
4.
5.
i 4 salts slightly more effective. NH 4 salts slightly lower (see Viscosity) Strong evidence that NH 3 & its salts are effective--no direct comparisons.
-j
\'-0 c-I
60
Emulsification, peptization
0\
TABLE VI (Continued) SUMMARY OF EXPERIMENTS INDICATING THAT NHX MIGHT BE THE DESIRABLE PULPING PROCESS IN COMPARISON WITH Ca, Mg AND Na See Page
Property or Consideration
Pro
Con
Undecided
Possibly of No Significance
10
7o
Coagulation effects
Slight tendency in favor of low coagulation Especially on alkaline side pH> 12--NaOH(l) alone in the field IH3 & salts lowest visc. morel than balances out surface tension consideration Some evidence that NH3 & salts have higher press
11
8.
Buffering capacity
11
9.
pH
12
10.
Viscosity--Capillarity, etc.
13
11.
Osmotic Pressure
13
12. 13.
Solubility of SO2 in aqu.soln. Higher Conc. with I'Ln3 as base !Il 3 & its salts Lower degradation of hemicellulose & cellulose fractions give the least Rapid delignification Some evidence that NH 3 gives higher rates Na close 2nd.
14o
(1)
This is significant in that it appears to limit the Kraft type of pulping to the Ra-base (or similar bases, e.g. K, etc.)