ammonium sulfite

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PROJECT REPORT FORMcc: Files

Dr. FormanMr. MacLaurinJohn Peckham

AMMONIUM SOLFITE PULPING

ROJECT NO. 1516COOPERATOR InstituteREPORT NO 1DATF July 14, 1950NOTE BOOK_ -PAGE--4 k-amSIGNED , C _/ John Peckham/ Notebook

38060289 6Pages

136-159

OBJECTIVE

The objective of this project is to investigate the ammoniumsulfite pulping process with emphasis on its application to certain speciesof hardwoods and the development of a recovery process for the spent cookingliquor.

ATTACK

Student pulping data from Course 203 will be used where appli-


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Page 2Project 1516July 14, 1950

EXPERIMENTAL

A portion of the gum wood was chipped while still in an unbleachedstate, and was begged without sorting or screening, At a later date anotherbatch was barked, chipped to a nominal 3/4a length chip, and these chips werehand sorted and fines which passed a 4-mesh screen were removed. Poplar andoak bolts were similarly processed Digester charges were prepared and thedry wood content was determined by oven drying representative portions ofthe woods.

The digesters used in this study were horizontal, rotary vessels,externally heatedbyb means of gas burners. No. 2 digester (of iron construction)and No. 3 digester (stainless steel) were filled with identical wood and liquorcharges and cooked simultaneously to provide adequate material for testing

The cooking liquor was made up by adding ammonium hydroxide to


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The cooked chips from the semi-chemical experiments were defiberedin the Bauer pulper using B957 plates. The chips contained warm cookingliquor when defibered and were diluted with tap water during the process toabout 8% consistency.

Washing was affected by draining the defibered stock on muslin-coveredwash boxes and replacing the liquor with warm water. This was repeated untilthe effluent was colorless.

Cook 1 was made on unbarked gum. The cooking conditions are shownin Table I. These conditions were demonstrated by the 1950 pulping classto be feasible for pulping to a yield of approximately 75%. A yield of74.5%was attained.

Cooks 2, 3, and 4 were made on peeled gum chips. The conditionsfor these cooks are also included in Table I. Cook 2 duplicated Cook 1 in


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TABLE ICOOKING CONDITIONS AND PRODUCT VARIABLESAMMONIUM SULPITE PULPING OF GUM AND OA K

Cook No. 1 2A 2B 3A 3B 4A 4B 6A 6BWood used Unbarked Peeled Peeled Peeled Peeled Peeled Peeled Peeled PeeledRed gum Red gum Red gum Red gum Red gum Red gum Red gum Oak Oa kWood moisture content, % 13.2 15.9 16.1 12.8 12.4 12.8 13.0 20.5 20,5Digester used No. 2,3 No. 3 No. 2 No. 3 No. 2 No. 3 No. 2 No. 3 No, 2RotaryDiges ter charge,O.D, basis, g. 3000 2998 2998 2998 2998 2998 2998 3144 3144Water ratio, O.D. Basis,cc./g. 4 O 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0Ammonia basis, O.D..Wood, 5.0 5,0 5.0 5.0 5.0 9.0 9.0 10.0 10.0so basis, O.D.Wood, 6.5 6.5 6.5 6.5 6.5 13.0 13.0 13.0 13.0Maximum temperature, C. 176 176 176 176 176 176 176 176 176Maximum pressure, p.s.i. - - - 158 164 162 155 166 16 0Time to max. temperature, min. 90 90 90 90 90 90 90 90 90Time at max. temperature, min. 30 30 30 120 120 120 120 120 120Relief time, min. 15 15 15 15 15 15 15 15 15Total time cover to dump, min. 135 135 135 225 225 225 225 225 225Unscreened yield, 74.5 74.5 67.2 63.2 57%5Black liquor datapH 8.0 8.3 6.2* 5.6 6.5 8.5 6.6* 8.1 7.3*NHE g./1. 9.2 9.6 1..5 8.3 10.4 16.8 16.4 19.8 15.7NH SO3 g./l. 0,21 0.29 o.45 Trace 005 7.9 21.4 18.5 23.4Total solids, % 8.6 o 1 9.8 9.4 ll.l 13.2 14.1 14..1 14.7Ash, % 0.16 O.12 0.17 0.15 O.21 0.10 .. 16 0.05 0.13Bauer dataFeed Sate 5 5 5 5 5 7 7 7Clearance, in .008 008 .08 08 .008 .008 .005 .005Load, amps. 480 48 480 500 500 450 450 350 350* Sample taken after blowdown


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Cook 5 applied most of the conditions used in Cook 4 topoplar chips. Details of this cook and all subsequent cooks on poplarare shown in Table II. The only variation was that 10% ammonia was usedinstead of the 9.0%applied in Cook 4, The chips from No. 2 digester weredarker than those from No. 3 digester, and the pulps were not mixed. Th eaggregate yield from the two digesters was 63.2*

Cook 6 was made using oak chips and the conditions of Cook 50The cooked chips from the two digesters were not combined because of thedarker color of those from Digester No. 2. The yield of pulp in thiscase was 57-5%.

Cook 7 was made on peeled poplar and utilized 15% ammonia and20% S02. The time at maximum temperature was 4 hours. Because the cookedchips appeared to be very soft, they were not defibered but were flushedfrom the digesters with water. The contents of the two digesters were not


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TABLE IICOOKING CONDITIONS AND PRODUCT VARIABLES

AMMONIUM SULFITE COOKS ON POPLARCook No. 5 5B 7A 7B A B 9A 9BWood used Peeled Peeled Peeled Peeled Peeled Peeled Peeled PeeledPoplar Poplar Poplar Poplar Poplar Poplar Poplar PoplarWood moisture content, 26.5- 26.3 22.7 23.5 23.8 22.6 23.9 23.7Digester used No.3 Rotary No.2 No.3 No. 2 No. 3 No.2 No.3 No.2Digester charge, O.D. basis, g. 2163 2163 2163 2163 2163 2163 2163 2163Water ratio, O.D. basis, cc./g. 4.0 4.0 4.0 4.0 4. 00.0 0 4.0Ammonia basis, OD. Wood, 0 . 150 1 5 5.0 15.0 15.0SO2 basis, O.D. Wood, 13.0 13.0 20.0 20.0 6.5 6.5 20.0 20.0Maximum temperature, 0C 176 176 176 176 176 176 160 160Maximum pressure, ps.i. 146 153 - - 144 155 118 118Time to maximum temperature, min.. 90 90 90 90 90 90 90 90Time at maximum temperature, min. 120 120 240 240 480 480Relief time, min. 15 15 15 15 15 15 15 15Total time, cover to dump, min. 225 225 345 345 105 105 585 58 5

Unscreened yield, 65.4 5.85 80.7 651.Permanganate number - 94 10.7 - - 19.2 21.7Black liquor data

Ph 8.6 6.6. 8,6 7.2* 7.2 6.2 9.25 6.75NH3. g./l. 18.2 19.3 26.2 26.6 10.5 11.3 32.0 23.5H4 2SO3. g./l. 18.0 19.6 33.6 46.7 9.2 11.9 27.6 32.8Total solids, 12.7 14.7 14.3 16.9 605 7.6 14.3 17.9Ash. 0.ll 0.12 0.07 0.11 0.09 0.12 0.10 0.13Bauer dataFeed rate 7 7 5 5Clearance, i.. o005 .005 - .005 .005

Load, amps. 250 250 - 320 320 -

* Sample taken after blowdown


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TABLE II (Continued)

Cook No.Wood usedWood moisture content,Digester used

10APeeledPoplar21.7No.3 Rotary

10BPeeledPoplar200No.2 Rotary

11APeeledPoplar11BPeeled

PoplarNo.3 Rotary No.2 Rotary

12PeeledPoplarNo.3 Rotary

Digester charge, O.D. basis, g.Water ratio, 0.D. basis, cc./g.Ammonia basis, O.D., Wood,SO2 basis, O.D., Wood,

Maximum temperature, 0 C.Maximum pressure, p.s.i.Time to maximum temperature, min..Time at maximum temperature, min.Relief time, mineTotal time, cover to dump, min.Unscreened yield, %

Black liquor data 7.69.54.47.30.08Bauer dataFeed rateClearance, in.

Load, amps.

74.11

7.005420

71.5 (72.8) 74.2

6.1511.34.09.40.14

8.919.618.28.70.127.005300

6.420.231.311.10.10

7005340

21634.05.6.5

12015225

21634.05.06.515 810990120

1522 5

21634.0100013.0

1581109012015225

21634.010.013.0

1581089012015225

21884.010.013.015810 99012015225

8.419.610.30.08


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Cook 8 was made on poplar using 5% HH3 and 6.5% SO2. The digestercontests were brought to 1760 C. in 90 minutes and cooking was halted Thecoateats of the two digesters were combined for defibering. A yield of8007 was obtained.

Cook 9 was made in an effort to obtain a well cooked pulp employinga maximum temperature of 160 C. The chemical concentration was 15 and 20%respectively for NH3 and S02. Time at maximum temperature was S hours. Thecooked chips were treated in the manner described for Cook 7. The screenedpulp from digester No. 2 had a permanganate number of 21.7. and that fromdigester No. 3 was 19.2. The aggregate yield was 65.1%.

Cook 10 was made with a further reduction in maximum temperature to158 C, The chemical concentration was 5% MH3 and 6.5% S.2, and the time atmaximum temperature was 2 hours. The cooked chips were combined before de-fibering. The yield was 74.1%.


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DISCUSSION OF RESULTS

The pulp from Cook 1 was made to provide a comparison of theammonium sulfite, neutral sodium sulfite, and semi-kraft pulping procedures inthe production of semi-chemical pulp for corrugating medium Progress Report 4.Project 1296 contains data on neutral sodium sulfite and semi-kraft pulps madefrom the same shipment of gum wood used in these experiments.Table III showsthe strength of these pulps as compared with the pulp from Cook 1. It will benoted that the ammonium sulfite pulp was slightly superior in all strengthproperties to either the sodium sulfite pulp or the semi-kraft pulps.

Beater evaluation data for the peeled gum and oak pulps are shownin Table IV. These data are plotted against beating time in Figures 1 through7. Table V compares the physical properties of the pulps at 700 cc. Schopper-


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Project 1516July 14, 1950

TABLE IIIFLAT SHEET TESTS AND CORRUGATING STUDY ON GUM PULPS

Pulp IdentificationCooking procedureYieldD

1516-1Ammoniumsulfite74.5

1296-1Semi-kraft

75.6

1296-19NeutralSodium sulfite74.5

Flat sheet testsBasis weight, 12x12-1000, lb.Caliper, pointsApparent densityBursting strength, pointsRing compression, lb.Elmendorf tear, g./sheet

Corrugating resultsDrawCaliper of single-face board, inoH & D flat crush, lb./sq. in.

Note: 1. Conditions for corrugating run on 1516-1 are included in Institute

29.410.82.74442100

1.5618820

26.10.22063523.298

1.5518318

29.29.92.94136.191

1.5418319


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TABLE IVPHYSICAL PEOPERTIES OF GUM AND OAK

AMMONIUM SULFITE PULPSCookWood used

Schopper-Rieglfreeness. cc*

Basis weight,(25x40)-500,lbo

Caliper, mils.

er 0*510152530354505

101525303545o5

1015

2PeeledRed Gum

885875845775490285

47.746.145.847.046.947.8

5.85.24.84.7

3APeeledRed Gum88585573540524545.545.746.646.546.35.14.74.1

3BPeeledRed Gum

87086075038521 046.246.445.846.546.15,34.94.2

4APeeledRed Gam

880840500165

8046.145.746.0

4.94.3

6APeeledOak

83576550017 0

47.246.547.2

5.2..7

4BPeeledRed Gum

885850590225110470546.546.646.8

6.46.0

6BPeeledOak

835765495170

46.1446.447.3

5.0.. 6


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Table IV (Continued)

CookWood used

Tear factor

Tensile,lb./in.

0*5

1015253545

05101525303545

2PeeledRed Gum

1.01.21.11.21.00.58.4

10.513.416.421.124.5

3APeeledRed Gum

1.31.51.31.00.79.513.2

21.826.1

27.5

3BPeeledRed Gu m

1.21.41.31.00.59.714.7

22.430.031 9

4APeeledRed Gu m

1.41.41.0

15.422.027.3

PeeledRed Gum

1.01.11.0o.70.7

10.714.721.124.9

6APeeledOak0.50.70.6

11.916.521.8

6BPeeledOak

0.60.70.7

12.516.722.5


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TABLE VPHYSICAL PROPERTIES OF GUM AND OAK AMMONIUM SULFITE PULPS

AT 700 CC. SCHOPPERE-IEGLER FREENESS

Cook 2 3A 3B 4A 4B 6A 6BWood species Gum Gum Gm Gum Gum Oak OakYield, 74.5 67.2 67.2 63.2 63.2 57.5 57.5Beating time, min. 18 16.5 17 10 115 8 8,5Apparent density 10.4 11.5 11.1 11.8 8. 10.4 10.6Bursting strength,pt./100 lb. 48 65 65 76 51 50 51Tear factor 1.2 1.2 1.3 1.2 1.0 0.7 0,7Schopper tensile,lb /in 17.8 22.7 24.0 25.8 19.3 18.3 19.0


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Page 21Project 1516July 14 1950

producing the pulp in digesters of different construction, Certainlythe darker color of the pulp from digester No. 2 can be laid to thechemical action on the iron shell.

The pulps from cooks 6A and 6B were alike in all respects.Apparently the difference in digesters had little or no effect on the qualityof the oak pulps.

A comparison of strength properties of peeled gum pulps atvarious 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. Little change was notedin tearing strength. Beating time to 700 cc. freeness increased with theyield,

Oak ammonium sulfite pulp was low in yield and in all strength


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The pulps from cook 5 were much higher in bursting strengththan the other poplar pulps, Other strength tests were as good or betterthan those displayed by the other pulps in this series. This is particularlyinteresting in view of the fact that cook 9 was made with a lower maximumtemperature, longer time schedule, and more chemical than used in cook 5,and was of approximately the same yield.

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 levelswhen poplar is the raw material. Bursting and tensile strengths appearto be somewhat higher in the general range of 62 to 72 yield, with de-creased strength on either side of this yield level. Tearing strengthseems to be affected comparatively little by yield variations.


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TABLE VIIICHEMICAL ANALYSIS OF AMMONIUM SULFITE(Basis oven-dry pulp)

Permanganate Alphanumber Cellulose, %10.0 71.8

~ 57.o19.2 69.421.7 68.l15.9 83.0

POPLAR PULPS

0.813.91.52.53.2

PentosansD

18.417.320.020116.4

* Student poplar kraft, Course 203-1940-41.

Cook

789A9B201*

Yield,

58.580.763.267.152.0


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The indications of these data are that the ammonium sulfiteprocess removes lignin more selectively than does the Kraft process, Cook9B, at 67.1% yield agreed quite well in lignin and alpha cellulose retentionwith the kraft pulp of 52% yield, but removed less pentosans. Cook 8,which had a yield of 80.7%, removed the least cellulose, lignin, andpentosans, but it is interesting to note that cook 9A which had a yieldof 63.2%, removed only 2.7%more cellulose and l .4%more pentosans thancook 8, while reducing the lignin 10.2%. Cook 7, which was more drasticthan cook 9A, indicates that in reducing the yield 4.7% lower than wasthe case in cook 9A, the cellulose content was reduced 1.9% and the pento-sans 1.56 while lignin was reduced only 0.5%.

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ONCLUS IONS

The work done to date on ammonium sulfite pulping seems tojustify the following conclusions:

1. The ammonium sulfite process gives a corrugating mediumpulp from unbarked red gum that is at least equal in yield and strengthcharacteristics to pulps made from red gum by the neutral sodium sulfiteor semi-kraft processes.

2. Ammonium sulfite pulps from peeled red gum are about equalin strength properties to red gum pulps of the same yield produced by theseni-kraft or neutral sodium sulfite processes. (The latter data fromStudent pulping course 203, 1947-1948).

3. In the yield range studied, (63.2 to 74.5%), ease of

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6. Mild cooking conditions (low temperature and long cookingperiods) did not increase poplar pulp strengths over pulps of similaryield made at high temperatures and short cooking times. In these experi-ments the reverse seemed to be true.

7 Ammonium sulfite poplar pulp of 10 permanganate number hada yield of 58.5% and was stronger in all respects than a sample of commercialpoplar acid sulfite pulp. Of note also is the fact that the ammonium sulfitepulp was more bulky than the acid sulfite pulp.

8. Data from Student pulping course 203 (1947-48) indicatesthat semi-kraft poplar pulps in a yield range of 60-65% are as strong asammonium sulfite pulps in the same yield level. Ammonium sulfite pulps in



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11. General conclusions as to cooking procedures are

A. that a tight seal is necessary on the digesters toinsure that loss of ammonia will not result in acook at a low pH. This is important because it isindicated that high pH is essential to developmentof maximum pulp brightness and quality.

B. iron equipment tends to darken ammonium sulfitepulp and may inhibit cooking

PROJECT REPORT FORM


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CC: FilesDr. FormanMr. MacLaurinMr. Madison

BLEACHING OF AMMONIUM SULFITE PULPS

The object of this portion of Project 1516 was to more or less brieflyinvestigate the bleaching properties of a few of the ammonium sulfite pulps de-scribed in Project Report One, and to find the effect of bleaching on strengthproperties.

Cooks 4A, 5A, and 7(A&B) were the pulps studied. By referring to ProjectReport One it will be found that Cook 4 was made on peeled red gum wood whileCooks 5 and 7 were on peeled poplar. The An nd "B" identifies the digester

I1

Page 2Project 1516


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Report No.2

TABLE ICOOKING CONDITIONS AND PRODUCT VARIABLES(Ammonium Sulfite Pulping)

Cook No. 4A 4B 5A 5B 7A 7BWood used Peeled Peeled Peeled Peeled Peeled PeeledRed Gum Red Gum Poplar Poplar Poplar PoplarWood moisture content, > 12.8 13.0 26.5 26.3 22.7 3 5Digester used No.3 Rotary No. 2 No. 3 No. 2 No. 3 No. 2

Digester charge, O.D. basis, g. 2998 2998 2163 2163 2163 2163Water ratio, O.D. basis,cc./.g. 4.0 4.0 4.0 4.0 4.0 0Ammonia, O.D. wood basis,% 9.0 9.0 10.0 10.0 15.0 15.0Sulfur dioxide, O.D. wood

basis, 13.0 13.0 13.0 13.0 20.0 20.0Maximum temperature, C. 176 176 176 176 176 176Maximum pressure, p.s.i. 162 155 146 153 - -Time to maximum temperature,

min 90 900 900 90Time at maximum temperature,

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Project 1516Report No. 2

The details on the way these pulps were handled after dumpingfrom the digesters may be found in Project Resort One. In summary, itmight be well to mention here that the pulps of Cooks 4 and 5 were runthrough the Bauer refiner while the more severely cooked pulp of Cook 7was 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 maximumcapacity was used for all chlorination. This chlorinator is equipped witha draft tube and a motor driven propeller type stirrer. A rotometer formeasuring the quantity of chlorine gas added to the stock is part of thechlorinating equipment. Subsequent caustic extraction and other stages werecarried out in five or ten-gallon crocks. Temperature control during bleach-

Page 4Project 1516


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Report No. 2

A 750-gram quantity of the pulp was bleached through chlorinationand caustic extraction stages. A portion of this two-staged pulp wa.s nextcarried through a calcium hypochlorite third stage and a final sodium chloritebleach was in turn given a part of this third staged pulp.

Table II gives the conditions during bleaching.General Electricbrightness sheets were made by Institute Method 412 and these results alongwith other dataare also given in Table II.

The results of tests made on British handsheets from unbeaten Cook4A pulp bleached as described here, and unbleached pulp as described inProject Report One are given in Table III.

This was the extent of the work done on Cook 4A pulp as far asthis report is concerned.


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Page 5Project 1516Report No.2

TABLE IIBLEACHING CONDITIONS

Pulp Used, cook No.WoodBleach No.

Chlorinati onPulp charge, g.Consis tency,Chlorine, O.D. Pulp weightbasis,Temperature, O C.Time to apply chlorine, min.Total time, min.Residual Cl2 at dump, g./l.

4AGum1

7503.007.002111.7730Trace

2 Caustic ExtractionPulp Charge, g. (all from 1st stage)Consis tency, 6.00NaOH, O.D. PULP WEIGHTbasis, b 50Temperature, o C.Yield through first 2 stages,% 91.3

5APoplar2

75035oo

11.7730O.142

6.002.50456091.3

.3 Calcium HypochloritePulp Charge, g.Consistency, %15 06.00 1506..o

12806.00

Stage

1

7(A&B)Poplar3

7503.003.002210 3730Trace

6.002.00456095.8

7(A&B)Poplar4

7303.003.002210.730Trace

6.oo2.00456095.9

Page 6Project 1516Report No. 2


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TABLE II (Continued)Pulp Used, Cook No.WoodBleach No.

4AGUm1

5APoplar24 Sodium ChloritePulp Charge, g.

Consistency,Available Chlorine, O.D. pulpweight basis,

Temperature,Time, min.pH

C.

703.00005

701203.8 (CH COOH used tolower pH)

4503000035 (av0 cl2O/S NaClO200.875% 01 2 G4565303.0 HCl used tolower pH)

Residual availabl l12 at dump,% of AppliedYield, start of 4th stagethru finish,4th stage, %G. E. BrightnessFiber slightly yellowand some dark shive

Fiber good white,less %hive thanafter 3rd stage

i

No.7(AB)Poplar

37(A&B)Poplar4

33.1

Notes:65.0 99.182.5

Page 7Project 1516


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Report No. 2

TABLE IIITEST RESULTS ON UNBEATEN BRITISH HANDSHEETS

Cook 4A (Gumwood) Cook 5ABleached Unbleached Bleached

Sheet Weight, g. 1.3063 1.296 ..3036Ream Weight (25x40--500). lbs. 46.2 46.1 46.3Caliper, in. 0.00420 0.0048 0.00324Mullen burst, points 24.85 17.8 43.30

Points/100 lbs. 53.5 39 93.7Apparent density 11.0 9.4 14 3

Bleaching of Pulp of Cook 7. A more extensive study was made onFirst, the bleach requirement of the pulp was found by InstituteBelow is data regarding these bleachability tests:

Poplar)Unbleached1.29846.20.003735.47712.5

this pulpMethod 409.


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Page 8Project 1516Report No. 2

this were a normal sulfite pulp, probably about 2.05 chlorine would be appliedinstead of 3.0.

As the capacity of the chlorination is only 1000 grams ovendrypulp basis when chlorinating at 3 consistency. two batches of 750 grams and730 grams were chlorinated and caustic extracted separately (Bleach 3 and 4)in order to be certain of sufficient pulp for subsequent work. The bleachingconditions are given in Table II.

After the caustic extraction stage, bleachability tests were runon Bleach 3 pulp under conditions which were to be adhered to in the finalbleach. General Electric brightness sheets were made at the end of the bleach-ing time. Data on this bleachability test is given in Table IV with brightnessresults.

Page 9Project


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1516Report 2

TABLE IVBLEACRABILITY TEST ON CHLORINATED ANDCAUSTIC EXTRACTED BLEACH 3 PULP,Cook 7 (M&B)

%Availble ChlorineApplied on Pulp

Weight Basis2.001.501.00

BleachingTime,m n300300300102

22

Consumed on PulpWeight Basis1.71

General ElectricBrightness,

84.584.31.35O.93

.50.25

84.077.870.7

Initial Brightness of Pulp

I

.2559.0


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Project 1516Report 2

Four hundred and fifty grams ovendry basis of this third stagecombined bleach 3 and 4 was next given a fourth stage bleach with sodiumchlorite. Conditions of this bleach are given in Table II. In order toobtain more efficient use of sodium chlorite chlorine gas in water solutionwas added to the bleach at the same time the sodium chlorite solution wasadded The chlorine gas was added in the ratio of one mol of the gas pertwo moles of sodium chlorite. The pH was lowered before the addition of thebleach with hydrochloric acid.

The bleached pulp of Cook 7 was given a beater evaluation afterthe third stage and after the fourth stage. Valley Beater No, 2 was usedfor these evaluations and a bed plate load of 5,500 grams was used

Table V gives the results of these beater evaluations along with

Page 12.Project 1516Report 2


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TABLE VPHYSICAL CHARACTERISTICS OF UNBLACHEDAND LEACHED PULPS OF COOK 7Pulp UsedBleach number Cook 7 (A B)Baw pulp Cook 7(A&B)(3&4)B3-s taged

Cook 7(AB)(3&4) c4-s agedSchopper-Riegler freeness, cc.

Basis weight, (25x40-500),lbs.

Caliper, mils. 0 3.75 3.310 3.115 2.925 2.6

0*510

1525

05101525

825735585390160

46.246.247l.46.546.5

810720570390170

46.746.446.246.5

810710520330150

46.546.446 56.5

3.43.23.02.83.53.22.92.9.8

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TABLE VIBRIGHTNESS VARIATION OF BLEACHED AMMONIUM SULFITE PULP

Pulp Identification: AvailableChlorine Applied

on Pulp vt. basis

1.501200.5O0.500.25

General Electric Brightness,June 22, 1950 June 23, 1950 June26

84.384.584.0770870.7

84.084.283.677.870.6

83.483.583.177.270.4

July 17,1950

8l.0

76.069.9

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It is not known if all this increase can be attributed to increasein apparent density and we simply have not enough information to make a state-ment of fact.

Table II shows that after the third stage the brightness of bleached4A Cook (Gumwood) was 60.9 and bleached 5A Cook (Poplar) was 1g.4. The relativeease of bleaching of these pulped woods cannot be compared by this data becauseit may be seen by referring to Table I, that while both woods were cooked with13.0 sulfur dioxide, the Gumwood was cooked with 9.0% ammonia and the poplar

with 10.0 ammonia. The Gumwood was thus given a less drastic cook, and itwas found more difficult to bleach. If the gumwood had been cooked exactly thesame as the poplar, it may or may not have bleached about the same.Again wehave insufficient data to know the answer.

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ammonium sulfite pulps made with chemicals of the approximate strength of thiscook (It will be recalled however, that Cooks 4A and 5A were Bauer refinedafter 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 easilybleachable.

It was stated before in this text that it was desired to obtain a bright-ness of 80 or greater on the third stage of this bleach. By referring to TableII it may be seen that a brightness of only 78.4 was obtained. This indicatesthat 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 attainedby applying available chlorine that in Figure I gave a brightness of about 82.

Page 16


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over the unbleached pulp while the tearing strength decreased in both casesbut slightly moreso for the sodium chlorite 4th staged pulp. In case oftensile strength, the 4th staged pulp was about the same as the unbleached but the3rd staged pulp dropped a small amount. The freeness curves indicate that the 4thstaged pulp with sodium chlorite was softer than either3d staged with calciumhypochlorite pulp r the unbleached pulp, the latter two being very nearly thesame degree of hardness.

If we refer to Figure III which enables us to compare strength resultsat constant apparent densities we find that again the bursting strengths forthe bleached pulps are about the same and are considerably higher than the burstingstrength of the unbleached pulpo The tearing strength shows decreases in boththe bleached pulps with the sodium chlorite bleach showing the greatestdecrease, In the case of tensile strength, the bleached pulps both are lower


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Page 20Project 1516Report 2


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With some investigation it may be found that good use could-be madeof bleached ammonium sulfite pulp in glassine, wax, some tissues, and possiblybook and bond papers. As may be concluded from this report, however , a greatdeal of experimental work must be done in order to obtain conclusive answers.


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INTRODUCTIODUT

The work covered in this report was divided into two parts. First wasthe investigation of possible chemical recovery methods that might conceivablybe employed with ammonium base cooking liquors. Efforts to e stablish a chemicalbalance from data collected for each of the cooks failed to account for morethan about 70% of the nitrogen applied. Cook 12 was therefore made for theprimary purpose of providing data and cooked chips that could be used in investi-gating the distribution of chemical in chips, black liquor and relief gases.

Page 2Project 1516


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Report 3

PRECIPITATION OF BLACK LIQUOR WITH SULFURIC ACID

A few test tube experiments showed that acidification of the amnoniumsulfite black liquor Produced a precipitate. Accordingly, a 200 ml. sampleof the liouor from Cook 7, containing 26.6 g./l. of ammonia, was acidified with5K[ sulfuric acid until no additional precipitate formed. After the precipi-tate had settled, a sample of the supernatant liquor was taken for determinationof ammonia. This determination showed the presence of 23.1 g. per liter ofammonia or a loss of 13.2% based on the original liquor.

PRECIPITATION BY SULFITITING BLACK LIQOUR

An experiment similar to that described above was carried out usingsulfur dioxide as the precipitant. In this case, the sample of black liquor

Page 3


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then allowed to settle for several hours. Treatment with additional sulfurdioxide showed that all the material was not precipitated so the entire samplewas resulfited for an additional 15 minutes. After standing overnight, atotal solids determination on the supernatent liquor showed 13.3% solids. Atotal solids determination at the same time on the original liquor showed 14.1%solids. Thus, 5.2; of the solids in the liquor were removed by the sulfitingprocess.

PPRECIPITTAION OF AMMONIUM SULFITE BLACKLIQUOR WITH CALCIUM OXIDE

Test tube experiments showed that addition of calcium oxide to blackliquor resulted in the formation of a slight precipitate. However, the presenceof the lime in the mixture made it difficult to determine how much precipitate

Page 4project 1516


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Report 3

AMMONIA RECOVERY BY VACUUM DISTILLATIIONThe possibility of ammonia recovery by application of vacuum to the

black liquor was investigated by the following experiment. A 300 ml. sampleof aronium sulfite black liquor (Cook 7) containing 26.2 grams per liter ofammonia was placedin a 2,000 ml. flask. The flask was connected through adistilling head to a trap containing a 4% boric acid solution. Vacuum wasapplied in such a manner that all the gas evacuated from the system passed throughthe 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 describedfor Determination of Ammonia in the Appendix. This tran contained only a traceof ammonia. Heat was applied to the distilling flask and roughly half of theblack liquor was distilled into the boric acid trap. The titration of thissecond trap shoved 0.06 grams of ammonia to be present. Because of the inadequacy


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Page 6Project 1516


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Report 3

to 0.87 grams.

Termperature,o C,10010 0

150-180160-230220-270270-320

gITHRecovered

2.49o.040.650.160.430.874.64 grams

2 1T Recoveredof3 Total

19.00.35.01.26.6

35.4 .

REPLACEMENT OF AMMONIA BY ADDITION OF LIMETO BLACK LIQUOR DURING SISTILLATION

Fraction

123456


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ammonia or 1.8% of the original. Another boric acid trap was placed on the systemand a sand bath placed under the distilling flask. The flask was heated forabout three hours at a temperature of 290 C. Nitrogen was passed through thesystem during this heating to carry the vapors through the condenser. Localizedheating in the sand bath resulted in melting the bottom of the flask towardthe end of the three hour heating period. For this reason the results insofaras the quantity of ammonia recovered in this fraction may be lower than thetrue value. The last boric acid trap contained 0.3 grams of ammonia or 6.85of the total ammonia in the sample.

Temperature, ETH , of TotalTrap Numberr Volume, ml. C. grams 31 106 100 0.9 23.42 57 100 1.6 42.13 29 100 0.1 1.8

Page 8


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pressure and all liquor had been drained from the chips, the cover of the digesterwas replaced and the chips cooled almost to room temperature before durning. Thecooked, drained chips were then weighed and a portion removed for experimentalwork. It was on this portion of cooked chips, the black liquor and theabsorbed relief gases that the complete nitrogen and sulfur balance was deter-mined.

A weighed portion of the cooked chips were covered with distilledwater and allowed to stand for 24 hours. The water was then drained and re -placed with fresh water and soaked over the weekend. In all, the water waschanged four times over a period of seven days. The chins were then defiberedwith the British disintegrator and the water removed from the pulp in a Buchnerfunnel. The nitrogen and sulfur content were determined on the leach liquorsand the filtrate and nitrogen only on the wood fiber. Sulfur was determined


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TABLE INITROGEN BALANCE -- COOK 12

A) Black l iquor through condenserB) Black liquor drained from chipsC) Relief condensateD) Boric acid trap -- relief condensateE) Boric acid trap -- black liquor relief [A above]

F) Boric acid trap -- top relief to zero p.s.i.G) Digester wash water

N2.grams39.114.37.10.00.0

1.90.4

o appliedof applied21.77.93.90.00.0

1.00.2

First leach liquor 62.9 34.9Second leach liquor 19.2 10.6



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TABLE IISULFUR BALANCE -- COOK 12

Sulfur, Sulfur,grams % of applied

A) Black liquor through condenser 32.2 22.6B) Black linuor drained from chips 12.1 8.5C) Relief condensate 0.3 0.2G) Digester wash water 0.5 0.4

First leach liquor 58.3 41.0Second leach liquor 17.0 12.0Third leach liquor 5.6 3.9Fourth leach liquor 2.0 1.4Filtrate from chip defibering 3.3 2.3

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Report 3

DISSCUSSION OF RESULTS

Of the several possible methods investigated for the recovery ofammonia front the black liquor, only one showed promise of presenting a feasiblesolution to the problem. The methods of precipitating solids from the liquordid not appreciably reduce the solids content. likewise the attempted removalof ammonia from the liquor by vacuum distillation removed but a small percentageof the ammonia in the liquor. The attempted recovery of ammonia from the liquorsolids by destructive distillation did not prove successful. However theequipment used was inadequate for this type of work. Local overheating andcharring of the solids resulted from the use of a sand bath for heating the distill-ing flask.

The one method that showed considerable promise was the replacement ofammonia by the addition of calcium oxide to the liquor. By this procedure, 65%of the ammonia present in the sample was removed before the liquor had been


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APPENDIX

Page 13APPENDIXReport 3-1516


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NITROGEN DETERMINATION

A) A 10 ml. sample of liquor was pipetted into a 500 ml. Kjeldalflask. To this was added 10 ml. of concentrated sulfuric acid, 10-15 gramsof sodium sulfate and 0.5 grams of copper sulfate. This was digested untilthe mixture in the flask ws light straw. olor to colorless, then continuedan additional 15 minutes In the case of the defibered wood, the quantitiesof sulfuric acid, sodium sulfate and copper sulfate were increased proportionatelyto compensate for the greater quantity of organic matter. After digestion wascomplete, the mixture was allowed to cool and solidify before continuing with

B) the second step in the procedure. The second stage consisted of distillation ofthe digested sample in the presence of caustic soda. The sample was dilutedwith about 200 ml. of distilled water and sufficient sodium hydroxide added tomake the solution alkaline. A Ejeldahl trap w s connected to the top of the


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MMONIETERMINATION

The determination of ammoniacal nitrogen in the black liquors wasidentical to the second stage of the method as described under NitrogenDetermination.

SULFITE DETERMINATION

A sample of the liquor to be tested was pipetted into a beakercontaining about 100 ml. of distilled water and sufficient ice to cool themixture. About 10 ml. of acetic acid were added plus a few drops of starchindicator solution. The solution was then titrated with 0.1 X iodine solution.

The titration for thiosulfate was the same as that described aboveexcept that 10 ml. of formalin was added to the solution before the titration.

Institute Tentative Method 109December, 1941


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ANALYSIS OF SULFATE BLACK LIQUOR

The composition of sulfate black liquor tends to change on standing,especially if access of air is permitted. Storage in. ompletely filledand stoppered bottles serves to arrest such change; however, the tendencyshould be kept in mind and, in general, the analysis should be startedand carried through without delay after sampling in order that resultsshall have maximum significance.Use recently boiled and cooled distilled water for all dilutions ofliquor sample throughout the analysis.1. GravityDetermine the Baume gravity of the sample at 60 F., by means of a suitablehydrometer. Convert to specific gravity, if desired, from tables or bythe formula:

Sp. gr. = 145- BaumeFor maximum accuracy, determine the specific gravity at 20 C. by meanc o fa pyonometer.2. Total Solids.Pipet 10 ml. of the liquor into a tared platinum evaporating dish andweigh quickly to the nearest 5 ng. Divide the weight of liquor by th especific gravity, thus obtaining a check on the volume of liquor delivered.

Institute Tentative Method 109-2

sulfuric acid has been removed Finnally, ignite t


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all the organic matter is destroued but again avoid excessive heating.Cool in a desiecator and weigh. Assuring the residue ot be pure na,so4calculate the sulfate ash to and report as per cent of the totalsolids . report the difference between this value and 100 as the percent of organic matter in the total solids.

4. SilicaMoisten the sulfated ash with 5 .. of concentrated HCl and, after abrief period. of contact, add 50 al. of hot water. Break up the residuewith 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 filterby screening the sides of he dish with a rubber policoman and finallywiping our with a pice of quantitative filter paper which is thenplaced In the filter with the rest of the residue Wash the residueon the filter with hot 1:20 HC1 and finally with water until the volu-metric flask is filled to the mark. Transfer the filter paper bearingthe residue to a platinum crucible, dry and smoke off the paper, and fin-ally ignite strongly to constant weight at 900 . or more. Cool in adesiccat or and weigh quickly. Moisten the ignited residue with 1 ml. ofwater, 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 hoodwithout boiling the liquid. When only sulfuric acid is left, increase



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6. Aluminum and Iron Oxides

By means of a pipet transfer a 50-ml. aliquot of the accurately dilutedfiltrate from the sil ica determination to a 250-ml. beaker. Dilute toabout 100 ml., add a few drops of Methyl red indicator solution andheat to boiling. Neutralize by dropwies addition of concentratedNH40H to the Methyl red end point (yellow) an, add a drop or two inexcess. Filter through a quantitative filter paper and thoroughly washthe precipitate, quantitatively transferred to the filter, with hotwater. Ignite strongly in a tared procelain crucible, cool, and weighas A1203 + F 203 .Calculation:Weight of ignited oxides x W7. Sodium Sulfate.Pipet 25 ml . of the original liquor into a 250-cl. baker containing about100 ml. of water and neutralize with HC1, adding 5 ml. of concentratedacid in excess. Filter and wash the precipitated organic materials thro-oughly with hot water, catching the filteato and washings in a 400-ml..beaker. Boil gently for 10 minutes and cool. Just neutralize to Methylorange by dropwise addition of concentrated NHIj,0H and then add 1 m . ofconcentrated HC1. Dilute to about 250 ml. and, with a stirring rod inplace to minimize the dancer of bumping heat to boiling. To thebriskly soiling soluticn, add dropwise and with stirring 15 ml. of 10per cent BaCl 2 solution. Maintain the solution near the boiling tempera-



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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. anddividing by the specific gravity. Add cautiously, a little at a Uime,about 4 grams of Na202. Guard against mechanical loss through efferves-cence by keeping the crucible covered with a small watch glass while th ereaction is actively progression. When all the sodium peroxide has beenadded , mix the contents of the crucible with a glass rod and finallyrinse off the cover glass, the stirring rod, and the sides of the crucibleinto 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 drynessand thereafter place the crucible in an electric muffle furnace or in asand bath over small flame. Heat slowly to a temperature not exceed-ing dull red heat until the organic matter is destroyed and the mass is inclear and quiet fusion. If this condition is not achieved, add anotherportion of sodium peroxide. Do not heat excessively. Remove the cruciblefrom the heat and rotate in an inclined position during cooling in orderthat tho volt is distributed over the sides and bottom of the crucibleupon coolidification. After cooling, dissolve the molt in water andfilter off any insoluble material, receiving the filtrate ald washingsin a 400-al. beaker. Just neutralize the solution to Methyl orange withHC and add 1 ml. of concentrated acid in excess. If a turbidity offree sulfur is formed on acidification, or if the odor of H2S is at allevident, the determination must be discarded and another made employinga larger proportion of sodium peroxide. Dilute the solution to about250-ml. and, with a stirring rod in place, boil gently for 5 minutes.Proceed further with the precipitation and estimation of the sulfate as



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during a titration. All electrical equipment except the electrodesmay be assembledd nd mounted in a convenient case. A 250- or 400-ml.neaker, preferably equipped with a mechanical stirrer, serves as thetitration vessel.Pipet 10 ml.. of the liquor a 100-ml. volumetric flask , dilute tothe mark and mix thoroughly. Place 150 LG. of water in the titrationbeaker and transfer 20 ml. of the diluted liquor corresponding to 2 ml.of the original) by ofn of a pipet to the noaker. The electrods mustbe completely submerged in the solution. If this is not possible withthe volume specified, more dilution water may be added. Start themechanical stirrer, switch on the apparatus, and adjust the rhecstateuntil teh a.c. ammoter reading is between 15 and 20 Note the readingon the voltmeter corrosponding to this initial setting. It is to bemaintained at the same constant value by readjustment of the resistancefor all ammeter readings during the subsepuent titration. Add standard0.1 N acid (HC1 or HE SO4 ) in small increments of 0.5 to 2 ml., dependingon the accuracy and the number of readings desired, and read the ammoterat constant voltage after each addition of acid until the titrationis complete. The end of the titration is reached when the rate ofchange in conductivity for 4 or 5 successive readins is constant andcharacteristic of the standard acid added.Plot the ammeter readings as ordinates against the volume of reagentadded. The final points obtainedhould define a straight line (theacid line). Preceding thi straight line segment ther will be a curveportion and preceding this final curve another linear segment shouldappear. the intersection of these projected straight line segments


Alternative Method for Total Alkali.


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Pipet 10 ml. of the liquor into an iron or platinum dish. Evaporate todryness and THEREAFTER ignite over a burner of perferably in an electricmuffle furnace. Heat slowly at first, finally bringing the temperatureto about 800 C. until the organic matter is decomposed It is unneces-sary to burn off all of the carbon resulting from breakdown of the or-ganic compounds. After cooling, take up the residue with 50 ml. of hotwater, breakin up the solid material as completly as possible with astirring rod. Filter and wash the residue on the filter with another50 ml. of hot water Titrate the filtrate with standard 0.5 N HC1 usingMethyl orange as the indicator. The volume of acid required representsan approximate value for either the total alkali or the total recoverablealkali, uncorrected for controversions duo to oxidation-reduction effectsaccompanying the incineration proccss and taking no cogniz incoof thesodium Silicate content.Calculation:

(uncorrected).dopending on the conditions of ignition, oxidation of sulfide and thio-sulfate to sulfate or the reverse process may occur, thus introducinguncertainty as to the exact significance of the above determinationTo provide for this situation, proceed as follows:Boil the solution which has been neutralized to the Methyl orange endpoint for 5 minutes to expel H2 S, cool, add a little starch-indicatorsolution and titrate with standard 0.1 N iodine solution. The amount ofiodine consuaic represents the thiosulfate content and the difference



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Taking cognizance of the fact that A and B as defined by the above maybe either positive or negative, correct the value for Total Alkalipreviously found by the following formula:Total alkali as grams of Na2O per liter (uncorrected) + 0.437 B + 0.392 A =

Total alkali as grams of Na20 per liter (corrected).As calculated, the corrected value for Total Alkali includes neither th ethiosulfate nor sulfate contents. A figure representing the TotalRecoverable Alkali may be derived from either the corrected or uncorrctAdvalue for Total Alkali by add ng respectively the thiosulfate and sul-fate contents (calculated to Na20) of the original liquor as separatelydetermined or the thiosulfate and sulfate contents as determined afterincineration. The result thus obtained for the Tot:l Recovera ble Alkalias well as the corrected value for the total alkali includes the sodiumsulfite and sodium silicate contents.B. Active Alkali (Na20 as NaOH and Na2S)Pipet 100 ml. of liquor into a 500-ml. volumetric flask partially filledwith 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 tosettle. Tost a small portion of the supernatant liquid for .excessprecipitant by adding a drop of dilute sulfuric acid. If no excess ispresent, repeat the preparation using a larger quantity of BaC1 2.Remove a 100-ml. portion of the supernatant solution and titrate poten-tiometrically, employing a glass electrode, with 0.5 N HC1 until a pHof 4 or lower has been reached. Prepare a titration graph by plotting



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10. Sodium Sulfide.By means of a pipet, remove a 50-ml. portion of the supernatant solutionprepared for the active alkali determination and transfer to a 150-ml.distilling flask equipped with a dropping funnel and connected on one sidethrough a wash bottle containing water to a tank of carbon dioxide ornitrogen and on the other, through the delivery arm and a condenser, totwo wash bottles containing an accurately measured volume of standard0.1 N iodine solution. There should be a substantial excess of iodine,the total volume used being at least 10 ml. more than that subsequentlyconsumed in the reaction with the .evolvod H2S, and the majority shouldbe placed in the first trap. A third wash bottle containing about 2 ml.accuratelyy measured) of standard 0.1 N thiosulfate solution serves toretain any iodine that might escape otherwise. The reagents in allthree traps may be diluted with water to afford an adequate depth ofsolution for officient absorption. Measure into the. dropping funnelby 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 requiredamount may be derivoed from the potontiometic titration carried out inSection 9. With the apparatus and materials completely assembled,swaesp outhe system with r moderate passage of gas for a few minutes(the gas inlet tube, with a constricted orifice, should extend belowthe surface of the solution). Temporalily discontinue the gas passageand lot the acid run into the sample, rinsing the funnel into the flaskwith about 20 m. of water and taking care that no evolved gas escapesthrough the dropping funnel. With the stopcock on the dropping funnelclosed, resume the passage of inert gas at about 2 small bubbles persecond and bring a becker or boiling water into position submerging the

Institute Tentitve Method 109-9


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miced thoroughly, and filtered through a Buchner funnel using suction.Test for complete precipitation of sulfide. Cool the filtrate in anice bath or refrigerator and pipot 100 ml. into a 500 ml. erlenmeyerflask containing 100 g. of ice. Add a few ml. of starch-indicatorsolution and sufficient acetic acid (predctermined by a rough teston 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) nd secure it in position with a rubber band.(This precaution is especially necessary if large amounts of sulfiteare present.) Puncture the rubber diaphragm with a noodle, insertthe tip of a buret containing standard 0.1 N iodine solution throughthe aperture thus provided, and titrate until the blue color producedon 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 ofice, add 10 m.. of formalin and swirl to mic. add starch and the sameamount of acetic acid as used in the first titration and titrate withstandard iodine solution until an end point of corresponding durationis reached. Call this titration B.Calculations:

Note:In general, the value thus determined for the thiosufate by this mathed


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AMMONIUM SULFITE PULPING OF WHITE BIRCH

INTRODUCTION

Consolidated Water Power and Paper Co. intermittently has troublewith pitch removal when pulping white birch. In investigating this problem,several experimental cooks were made on white birch chips, utilizing ammoniumsulfite or sodium base sulfite as the pulping agent. The present reportcovers the procedures used in making these cooks and the results of tests madeon the produced pulps.

RAW MATERIALS

Project 1516Report 4June 24, 1952Page 2


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Pulping Group Procedure 40. Moisture determinations made while dividingthe chips into individual charges showed 20.07% moisture in the chips. Asit became evident that additional chips would be required, a second lot ofwood was chipped and digester charges were prepared as above. This second lothad a moisture content of 19,88%. Cooks 17 through 20 were made from thefirst lot; the remaining cooks were made from the secondlot.

All pulping experiments were carried out in stationary, verticaldigester No. 4. The capacity and characteristics of this digester are outlinedin Pulping Group Procedure No. 40.

The cooking liquor used in making the first cook (Cook 17) wasprepared by dissolving ammonium sulfite crystals in water and adding sufficientammonium hydroxide to achieve the desired ammonia concentration in the liquor,



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into the blowpit. The remainder were washed from the digester through theblowline using a jet of hot water, The chips were quite hard and were notdisintegrated during the standard washing procedure. A small portion of thecooked chips was disintegrated in the 8-inch laboratory Bauer and then screenedin the Valley flat screen using a o. 10-inch cut plate. The permanganatenumber of the screened pulp was found to be 332 (determined according toInstitute Method 410 - 40-cc, basis).

It was felt that the bad liquor leaks encountered in the previouscook were partially responsible for the lack of pulping found. The cook wasduplicated, therefore, in all respects except the cooking liquor. In thiscook (Cook 18) the liquor was prepared by bubbling sulfur dioxide gas throughammonium hydroxide. The S02 content of the liquor was determined according tothe Palmrose method, and the ammonia content was determined by the Kjeldahlmethod. No attempt was made to adjust the liquor to the desired ratio of S02



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The cook was blown at an assumed pressure of 80 ps.i,, but againonly a very small portion of the chips were removed from the digester. Theremaining chips were washed from the digester using a jet of hot water. Asin the previous cook, the chips were very hard and had to be disintegratedby passing them through the 8-inch Bauer. Only sufficient pulp was de-fibered and screened to determine the permanganate number and the percentageof ether extractables. This latter test was carried out according to Insti-tute Method 427, eliminating the alcohol extraction. The results of the abovetests 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. Becauseof the difficulty encountered with the previous cooks in washing the rawcooked chips from the digester, a stainless steel basket was used for sub-

Project 1516Report 4June 24, 1952Page


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TABLE ISUMMARY OF COOKING CONDITIONS AND PRODUCT VARIABLES

(Cooks 17 - 21Raw Material: White Birch

Cook No. 17Applied chemical SO, % 20

Imj* % 15Water ratio (OD), cc./g. 5.1Cooking Schedule:Max. pressure, p. si. 80Time to max., hr. 3Time at max., hr. 13Temperature found at max.press., 0C157Time of incrase ot60 C hr.

1820156.0

80313

1920156.0

803

13

14912

2020156.0

803

13

1494

2130*166.0

803

13160


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be 8.0. During the early part of the cook, the pH dropped quite rapidly, reach-ing 7,1 in 0.75 hours cooking time. From this point the drop in pH was notas rapid. A pH of 6.4 was reached after 8 hours cooking and this conditionwas maintained throughout the remainder of the cook.

The pulp obtained from this cook was much softer than any of theprevious pulps and it defibered quite readily during the washing operation.The washed pulp was screened, without further mechanical defibering. Approxi-mately 10-15% of the pulp was rejected by the screen. The rejects were de-fibered in the 8-inch Bauer and rescreened, the through-fraction being combinedwith the screened pulp obtained from the original screening operation. Therejected portion from the second screening represented less than 0.04% of thepulp produced. Results of tests made on this pulp are shown in Table I.

Report 4June 24, 1952Page 7


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1.01% combined SO2. A maximum temperature of 148C. and a maximum pressureof 80 p.si. were used. Total cooking time was 8 hours, using 3 hours to reach110 0C., 3 hours from 110 to maximum temperature and 2 hours at maximum temper-ature. Final relief to atmospheric pressure was extended over the last 1.25-hours of cooking time.

hem the digester was relieved to atmospheric pressure the cover wasremoved and the basket containing the top half of the chip charge was liftedout. These chipsere dumped into a blowpit and washed according to the standardprocedure.

All liquor was drained from the chips remaining in the digester. Thiswas accomplished through the liquor line, leaving the blow valve intact.After the liquor was drained, the drain valve was closed and 9 liters of hotwater was poured over the chips. This amount of water gave good chip coverage.



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TABLE IISUMMARY OF COOKING CONDITIONS AND PRODUCT VARIABLES (Cooks 22 & 23)Raw Materials White Birch

Cook 22-1 22-2* 23Liquor analysis: Total SO , 7.18 6.55Free SO2 % 6.17 - 530Combine S02, % 1.01 -- 1.25Liquor ratio, cc./g. (ovendry) 6.0 -- 6.0Cooking Schedule:

Time to 110.C., hr. 3.0 - 7.0Time, 110C. to max., tempo, hr. 3.0 0.25 5.0Time at max. temp., hr. 2.0 1.0 4.0



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The final cook carried out under this program to date was a soda-basesulfite cook using a long-cooking scheduled A liquor ratio of 6.0 cc./g. ofovendry 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 bothpulping and pitch removal. In some cases good pitch removal was obtained, but

the conditions employed were too mild to produce a good pulp. Where good pulpswere 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

MEMORANDUMFrom D. J. MacLTo The Files Date May 13, 1954


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Subject Project 1516 -- Institute (Ammonium sulfite pulping)

About a year ago it was decided that a thorough review of the literatureshould be made with respect to all aspects of ammonia and ammonia compoundsas pulping agents. It was further decieed that this review should leadto two reports--the first report classifying the relevant literature on asubject basis, and a second report reviewing the literature critically--for the purpose of pointing up the inadequacies in our knowledge and under-standing of ammonia and ammonia compounds as pulping agents, and thusoutlining 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 thisproject file as Project Report 4 A report dealing with the second phaseof the literature survey was completed about the end of 1953, and isincluded in the file of this project as Project Report 3.6

djm/jh

PROJECT REPORT FORM

cc: The FilesMacLaurin


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Helleur

CLASSIFICATION OF AMMONIA-BASE PULPING LITERATURE


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CLASSIFICATION OF AMM ONIA BASE PULPINGLITERATURED. E. HELLEUR

A comprehensive condensed classification of the ammonia-base pulping literature 1900 to June, 1953) is presented.Some 85 articles and 47 U. S. patents are classified fromvarious points of view, having in mind the interests of boththe mill and the laboratory.

AMMONIA-base pulping is not new The firstpatent was issued to Braun in 1902 (34, 69, 100). Inrecent years, not only has it been receiving increasingattention and interest but it has also been used fairlyextensively to produce commercial tonnages of pulp.The major part of this use and interest has centeredaround the ammonium bisulphite process.To aid those who are interested in the literature ofthis particular field, references have been collected andclassified for the period 1900 to June, 1953. In classi-fying these references, an attempt has been made toanticipate the interests of both the operational and tech-nical approaches to the subject. No attempt has beenmade to review the material critically. Reference

COOKING PROCESSESAmmonium Hydroxide

Konig Process. Wood is heated with ammoniumhydroxide and this treatment is followed by treatmentwith a mineral acid (or vice versa ) (101); a furtherpatent 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 thesaponification of casein to obtain a product which undercertain conditions of pressure and temperature evolvesnascent ammonia which can be used for cooking fibrousmaterials. Merits and demerits are discussed in (8 ,29).

Billwiller. A broad patented process making use ofsuch cooking chemicals as ammonia, sodium carbonate,hydrogen sulphide, etc., with the emphasis on the use ofcatalysts and of a pretreatment using these chemicalsfollowed by known cooking processes (i.e., prior to 1919)

131, 134, 140,141, 142, 143, and 146). See also (I, IV,VI, IX, X, XIII) under miscellaneousUsing a liquid sulphur dioxide pretreatment (on long-leaf pine) followed by the bisulphite (57). Commentson this study (65); others (7, 10, 11 20, 35, 38).General reviews covering the process are (17, 34, 38,

bases including ammonia (63); an industrial review ofthe sulphite (acid) process including evaporation ofliquors (ammonium included) (79); comparison of thevarious sulphite pulping methods from the point ofview of the spent liquors (71).Evaporation


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85).Miscellaneous Cooking Processes

(I) Gaseous Cooking. Sammet and Merrill treatfibrous materials with gaseous ammonia and sulphurdioxide and steam (103); a gaseous pretreatment lab-oratory trial (16).

(II) Using ammonia and steam only, there are (76,139).(III) A somewhat novel way of arriving at an am -monium sulphite cooking liquor is to treat a calciumbisulphite solution with ammonia, thus forming an am -monium sulphite solution with the precipitation of cal-cium sulphite. The fibrous material is then cooked withthis 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 orcyanate which forms ammonia by saponification withwater; supposedly, the difficulties in the decomposi-tion of wood by ammnoium hydroxide are therebyavoided (115).(VI) Another very broad patent covers pulpingwith ammonia and sulphur dioxide as well as the sul-phite, sulphate, carbonate, and sulphide salts of am -monium either separately or in combination; for cer-tain wood the ammonium bisulphite is preferred; formaterials like cotton linters, amnona; agricultural

Under pressure to recover chemicals (130, 133). Anallied subject is concentration by recycling (144).Evaporating and Burning Recovery of Heat)

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 blackliquor (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 vacuumevaporation (52).Sulphur Dioxide. Commercial trials, sulphur dioxideliberated during the burning step (14,61,81); recoveredduring evaporation (130, 133).Ammonia and Sulphur Dioxide. Processes claimingto recover both: Solvay process (71, 133); by boilingunder pressure at approximate 40% concentration(137); by boiling to liberate sulphur dioxide, then addi-tion of a base to liberate ammonia (133); by a processof pyrolysis on the concentrated solution or the drysolids (138); pertinent to this latter process is (53);treating with magnesia to liberate ammonia and toconvert liquor to magnesium base, evaporating andre-

3 Crown Zellerbach Corp., Lebanon mill (also pilot plantstudy of evaporation and burning the spent liquor) (14,51, 61, 81).4. Diamond Match Co, Ogdensburgmill (37).5. Eastern Corp., Lincoln and South Brewer mills (51).6. International Paper Co., Southern Kraft Div. (48).7. Rayonier, Inc., Shelton, Wash (3, 5, 33, 51, 65).8. Toten Cellulosefabrik, Nygard (Norway) (24, 35, 51, 75).9. Wausau Paper Mills Co., Brokaw, Wis. (2, 82).

NI sulphite waste liquor. Tappi 34, No 3: 126-131(March, 1951); B I P.C. 21: 584, C A. 45: 4447.2 Ammonia in more mills; liquor burning at Badger and[ntellake Pulp & Paper 25, No. 3: 64 (March, 1951);RI P C 21: 585.3. Ammonia pulping report. Paper Ind. 33, No. 12: 1438-1439 (March, 1952); B.I.P.C. 22: 614.4. Aries, Robert S., Recent developments in the utilizationof sulphite waste liquors. Northeastern Wood UtilizationCouncil Bull. No. 14- 97-121 (Jan, 1947), B.I.P.C. 17:


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Organization and implementation of an ammonia-base trial discussed (34) Design of ammonia-basesulphite acid systems (42, 43, 44,45,54,82,83). Prep-aration of raw cooking acid (13) Digester linings(78). Corrosion of linings (40). Review of the fieldand a report of the progress (48, 49, 65, 72, 75).

ANALYSIS, TESTING, AND GEN Eral CIIEMISTIRYTesting of the cooking liquor with a modified Palm-

rose method (13). Conductometric analysis of thepulping liquors for such as ammonium hydroxide, car-bonate, sulphite, bisulphite, and acetate (84).

Sulphite process (22, 26, 27, 32, 36, 56, 58). Chemis-try of reactions, cooking variables, etc., kinetics of,penetration studies (16, 19, 36, 39); ammonia pretreat-ment (16, 59); system: ammonia, sulphur dioxide, andwater (42, 43, 44, 45); cooking liquor (56); spent liquor(27, 32).

ADVANTAGES CLAIMED FOR AMMONIA-BASEPULPING

Claims and comparisons together with their refer-ences are listed below. Many of these claims, it willbe noted, are not specific to ammonia-base but exist onlywhen taken in comparison with some other base. Prac-tically all the claims are made with respect to the am-monium bisulphite process.1. Ease of raw material handling (i.e., cooking

380.5. Aries, Robert S., Research on lignin as a soil builderNortheastern Wood Utilization Council Bull. No. 7: 56-62(Oct. 1945'; C.A 40: 1623; B I.P.C. 16: 183.6. Arnot. J. Melrose, Some new processes for the separationof fibrous cellulose from plant substances. World's PaperTrade Rev. 95, No 11: 961-962, 964 (March 13, 1931);B.I.P.C. 1, No. 9: 20.7. Aronovsky, S. I, Ernst, A J.. Sutcliffe, H. M, and Nelson,G H. Agricultural residue pulps-comparison of pulpingprocesses 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: 790.8. Barbier, Emile, Imitation kraft paper from straw by meansof the so-called Gluteor process. Papetcie 49, No 12:538-543 (June.25, 1927); T.S. 86: 7; C.A. 21:2984.9 Benson, Henry, K, Ammonia pulping of wood. Pulp &Paper24, No. 8:74, 76 (July, 1950), B I P.C. 20: 907.10 Benson, H. K., Erwin, R. P, Hendrcklson, .1. R., andTershin, J. A., The pulping of Douglas-fir by ammonia-baseliquor. 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: 46.11. Benson, H. K., and Lucas, J. E , The pulping of Douglas-fir 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. 11:35.12. Billwiller cooking process. Zellstoff Pape 11, No. 4:197 (April, 1931); T.S. 94: 3.13 Bishop, F. F., and Honstead, J. F, Ammonia-base sulphitepulping liquors-their preparation and analysis. Tappi34, No. 7:318-323 (July, 1951); C.A. 46:255; B.A. 1951B,II: 1009: B I.P.C. 21:877.14. Booth, Kenneth, G , Ammonia sulphite process. Pulp &Paper 26, No. 9: 80, 82, 84 (Aug, 1952); B.I.P.C 23: 754.15. Brot, M V., and Hirschel, M., Treatment of straw and ofwoods ith sodium sulphite and ammonium sul-phite. Papier29, No 1 75-80 (Jan , 1926); Paper Ind.8, No. 1:97, 99, 101 (April, 1926); '.S 83: 100; C.A. 201322.

27. Dorce, Charles, and all, Leshe, The hgnosulphonic acidobtained from sprucewood by the action of sulphurous acidin the presence of ammonia .. Soc. Chem. . 44, No.23: 270-274T (June 5, 1925), C.A 19: 2742.28. Engelstad. Alfred, the Cross and Engelstad process forcooking cellulose with sulphurous acid solution in the pres-ence of ammonia PaprJ. 19, No. 5: 58-60, No. 6: 67-69 (March 31', April 15, 19:31); C.A. 26: 4711.29. Fournier, Raymond, Imitation kraft by the so-calledGluteor process. Papeterie 50, No. 4: 170, 173-174 (Feb.

51. LaFond, L. A, and olzem, F., Commercial sulphiteproduction experience with ammonia-base acid. Tappn34, 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 , Commposi-tion changes occurring during vacuum evaporation, steamstripping. and de-ashing of ammonium sulphite liquorsTech. Assoc. Papers 31. 236-238 (June, 1948), PaperTrade 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


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25, 1928), T.S. 87: 23830. Frank, - -, Quality of the cellulose prepared by the Konigprocess. Papier-Ztg. 39, No. 17: 571 (Feb. 26, 1914);Wochbl Papterfabr. 45, No. 13: 1118-1121 (March 28 ,1914); C.A. 8: 1502.31. Froberg, A., Konig's new process for the manufacture ofcellulose Wochbl Papierfabr 44, No. 47:4432-4434 (Nov.22, 1913);.1. Soc. Chem Ind. 32: 1152; C.A. 8: 2802.32. Hgglund, Erik, Chemistry of sulphite cooking. SvenskKern Tid. 38, No. 7:177-192 (July, 1926); Papier-Fahr. 4,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, 911.33. Hatch, Raymond, S , Comparison of possible bases forsulphite pulping-economics of recovery. Pulp PaperInd.21, No. 4: 42, 44, 46, 48 (April, 1947); Pulp PaperMag.Canada 7, No. 9:80-84 (Aug. 1946); C.A. 40: 6812; B.A.1946B, II: 456, 1948B, 11:24; B I.P.C. 17: 153.34. J., Alkalies as bases for sulphite liquor. Papier-Fabr.24, No. 45: 691-695; No. 46: 709-713; No. 47: 722-728 (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: 171.35. Hazelquist, Svarre E., Innovations in Sweden and Nor-way. Pulp Paper Ind. 20, No. 13: 58 (Dec., 1946);B.I.P.C. 17: 245.36. Hepher, W. S., and Jahn, . C., Action of ammonium sul-phite 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: 98.37. Horton, J. L, Organization and implementation of anammonia-base mill trial. Pulp Paper Mag. Can. 54, No3: 205-209, 214 (Convention, 1953); B.I.P.C. 23, No.8: 584.38. Houghton, E. O., Ammonium bisulphite-its use as a basein 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: 167.39 Howell, Charles, M., and Cunningham, Eugene, L, Iffectof chip dimensions on penetration of ammonia-base cook-

53. Markham, Aaron, 1 , Peniston,Quintin P..and McCarthy,Joseph, L , The pyrolvsis of ammonium sulphite wasteliquor to yield ammonia. Tech. Assoc Papers 31: 407-411 (June, 1948); PaperTade 1. 127, No. 64-68 (July 1,1948); C.A. 42: 7040 B A 1948, I: 390, B. P.C. 1887 154. Marriner, D. E , and Whitney, Roy, P., The solubility ofsulphur (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; B .I C 18: 713. See alsoTAPPI data sheets 148C-148D (Dec., 1948)55 Martin, . , Utilization of NI-lbase SO1 liquor. Tappi36, No. 6: 175-176A (June, 1953:); Proc. 4th Ann. Pac NWInd. Waste Conference Washington State Inst. of Tech.,Washington State College56. Marusawa, Tsuneya, Constitution and stability of variousliquors used in the sulphite process and their specificationin 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 sulphurdioxide process for sulphite pulp. III. Character of pulpobtained from extracted longleaf pine chips. Paper TradeJ. 80, No 17: 41-46 (April 23, 1925): C.A. 19: 1947; T.S.81: 136.58. Mottet, Arthur L., The sulphonation of western hemlocklignin. Pac. Pulp Paper Ind 13, No 10 22-25 (Oct.,1939), B.I.PC. 10: 12159 Moulton, . W and Ziegler, J. G., Study of the effect ofNH, pretreatment on pulping of resinous woods. U. ofWashington thesis (19:32)6O Palmen, John, The cooking of spruce chips with sulphurdioxide solutions of high concerntiation Finnish PaperTimber .. , 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 ofheat and sulphur from spent ammonia-base sulphlte pulp-ing liquor. Tappi 35, No 5: 193-198 (May, 1952);

73 Stops. Paul, A survey of some pulping methods. Proc.Australian Pulp Paper Ind Tech. Assoc. 1: 154-165; dis-cussion, 165-168 (Dec., 1948); B.A. 1948B, 11: 606; R I.P.C. 19: 12.74. Sulphite mill cooks with ammonia base in Norway; anotherwith soda base in Sweden. Pulp Paper nd. 19, No. 10: 24(Oct, 1945); B.I.P.C. 16: 165.75. Sulphite pulp may offer postwar ammonia market. Chen.Ind. 55, No. 5: 818 (Nov., 1944), B I.P.C. 18: 186.76. Svenska Pappers- och Celluloseingenidrsforeningen. Pulp-

1923109. Cross, Charles F, and Engelstad, Altred, Wood pulp.Brit. pat. 229,002 (Nov. 15, 1923); Ger. pat. 495,146 (Oct23, 1924); Fr. pat. 588,071 (Oct. 25, 1924), C.A. 19: 3018:T.S. 82: 251.1925

110. Cross, Charles, F., Manufacture of wood pulp and by-products. U. S. pat. 1,547,907 (July 28, 1925); C.A. 19:3018; T.S. 82: 235.


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ing of wood with ammonium bisulphite according to Engel-stad Tekniska Meddelanden TB 2 (June, 1940), 1 page.77 Thode, E F., and Lee, Y. H., Ammonium-base sulphitepulping of hardwoods. Tappi 33, No. 6: 257-260 (June,1950; B I.P.C. 20: 816.78. Tucker, F.. Digester linings for soluble-base sulphitepulping Tappi 33. No. 1: 29-32 (Jan., 1950); B.I.P.C.20: 393.79. Vincent, Rex , Position of the sulphite (acid) process in thechenmcal and paper helds (industrial review) and bibliog-raphy. Also evaporation of liquors, hardwoods. PaperTr 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 16:370.80. Waddell, R D, Ammonia-base process-evaporating andburning at Lebanon Pulp & Paper 25, No 11: 58 (Oct.1951); B I.P.C. 22: 205.81. Waddell, R D., Ammonia-base sulphite mill. Pulp &Paper25, No. 8: 56, 58 (July, 1951); B I.P.C. 22: 205.82. Wausau's new acid plant in full operation. PaperTrade J136 No. 23: 10 (June 5, 1953); Paper Mill News 72, No23: 6 (June 6, 1953); Paper Ind. 35, No. 4: 423-424 (July.1953)83 Whitney, Roy P , and I, S. T, Design basis for am-monia-base sulphite raw-acid towers. app 35, No. 12:569-576 (Dec. 1952), B I P C. 23: 309.84 Whittemore, E. R, Divden, E. C., and Aronovsky, S. I.,Conductometric analysis of sodium sulphite and ammoni-acal 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. 11:396.85. Yorston, F. H., Use of ammonia in sulphite cooking. PulpPaperRes Inst. Canada.LaboratoryRept. No. 27 (1943-44).

I

1927111. Billwiller, John, Method of loosening vegetable fibers.U. S. pat. 1,649,281 (Nov. 15, 1927); T.S. 87: 238; C.A.22: 500.112. Ekstrom, P. G., and Hult, R H., Process for the manufac-ture of sulphite pulp from wood or other fibrous materials.Swed. pat. 68,741 (Sept. 26, 1927), T.S. 91: 275.

1929113. Michael, Wilhelm, and Palm, Albert, Recovery of sulphitewaste 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: 4246.114. 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: 2780.115. Sido, Otto, and Wiederhold, Hermann. Process for the pro-duction of cellulose. Ger. pat. 505,589 (Aug. 18, 1929);T.S. 93: 174; C.A. 25: 593.1930

116. Baker, Webster E. B., Sulphite wood pulp and method ofmaking the same. U. S. pat. 1,773,419 (Aug. 19, 1930);C.A. 24: 5158.117. 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

118 Benson, Henry, K., Process for making sulphite pulp fromDouglas-fir and other resinous conifiers. U. S. pat. 1,805-799 (May 19, 1931); C.A. 25: 3825; T S. 94: 126.119. Hixon, Ralph M., Peterson, Charles J., and Werkman,Charles H., Process of pulping plant tissues by means of avolatile base. U. S. pat. 1,802,715 (April 28, 1931); T.-S. 94: 123; C.A. 25:3836.120 Richter, George A., Process for the production of chemicalwood pulp. U. S. pat. 1,817,525 (Aug. 4, 1931); Can. pat.

131. Richter, George A., Fiber-liberating process. U. S. pat.2,032,437 (March 3, 1936); C.A. 30: 2759; T.S. 103: 248.132. Richter, George A., Process of correlating chemical recoveryin 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

133. Norsk Hydro-Elektrisk Kvaelstofaktieselskab, Recovery

1941141. 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.

1942142 Sheldon, Lyle, M., Cellulose pulping system. U. S. pat2,300,733 (Nov. 3, 1942).


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sulphur dioxide and ammonia from waste liquors. Nor.pat. 58,194 (July 19, 1937); C.A. 31:8926.134. Olsen, Fredrich, Cellulose pulping system and productthereof. U. S. pat. 2,087,263 (July 20, 1937); C.A. 31 -6464; T.S. 106: 130; B.C.P.A. 1940B: 199.135 Saft, Juljusz, Cellulose. Fr. pat. 817,852 (Sept. 13,1937); C.A. 32: 2351.

1938136. Kovats, Lajos, Pulp. Hung. pat. 119,466 (Nov. 15, 1938);C.A. 33: 3149.137. Norsk Hydro-Elektrisk Kvaelstofaktieselskab, Working upwaste ammonium bisulphite liquors. Nor. pat. 59,229(April 11, 1938); addition to 58,781 (Jan. 3, 1938); C.A.32: 7264.138. Norsk Hydro-Elektrisk Kvaelstofaktieselskab, Sulphitewaste liquor treatment. Fr. pat. 823,778 (Jan. 26, 1938);T.S. 109: 62.139. Waeser, Bruno, Pulping cellulosic material. Ger. pat.658,686 (April 11, 1938); C.A. 32: 6462.

1939140. Richter, George A., Cellulosic material pulping process.Can. pat. 382,892 (July 25, 1939).

1950143. Jesseph, Donald C., Stable bituminous emulsion and prep-aration thereof. U. S. pat. 2,494,708 (issued Jan. 17 ,1950). 4 claims. C.A. 44:3706; B.I.P.C. 20:768.

1951144 Parrett, Arthur, N.. Wood pulp digestion. U. S. pa t2,564,028. Filed Jan. 17, 1946. Issued Aug. 14, 19513 claims. Assigned to Rayonier, Inc., (Cl. 92-11); B.I.-P.C. 22: 87.

1952145. Andersen, Carl C., Treatment of waste sulphite liquorCan. pat. 481,243. Filed Aug. 21, 1939. Issued Feb19, 1952. 2 claims. Assigned to Norsk Hydro-ElecktriskKvaelstofaktieselskab; B.I.P.C. 22: 643.146. Helleur, Dotiald, Treatment of the spent cooking liquor olan ammonia-base sulphite pulping process. U. S. pat2,596,241. Filed Dec. 20, 1948. Issued May 13, 19524 claims. Assigned to Price Brothers & Co., Ltd. (C l23-129); B.I.P.C. 22: 799.

The Institute of Paper Chemistry . .MEMORANDUMFrom D. J. MacLaurinTo The Files Date May 13, 1954Subject Project 1516--Institute (Ammonium sulfite pulping)


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About a year ago it was decided that a thorough review of the literatureshould be made with respect to all aspects of ammonia and ammonia compoundsas pulping agents. It was further decieed that this review should leadto two reports--the first report classifying the relevant literature on asubject basis, and a second report reviewing the literature critically--for the purpose of pointing up the inadequacies in our knowledge and under-standing of ammonia and ammonia compounds as pulping agents, and thusoutlining 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 thisproject file as Project Report i A report dealing with the second phaseof the literature survey was completed about the end of 1953, and isincluded in the file of this project as Project Report 3

djm/jh

PROJECT REPORT FORM

cc: The FilesMacLaurinHelleur


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CLASSIFICATION OF AMMONIA-BASE PULPING LITERATURE

PROJE T REPORT FORM

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CLASSIFICATION OF AiMMONIA-BASE PULPING LITERATURE

CLASSIFICATION OF AMMO NIA BASE PULPING


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LITERATURED. E. HELLEURA comprehensive condensed classification of the ammonia-base pulping literature 1900 to June, 1953) is presented.Some 85 articles and 47 U. S. patents are classified fromvarious points of view, having in mind the interests of boththe mill and the laboratory.

AMMONIA-base pulping is not new. The firstpatent was issued to Braun in 1902 (34, 69, 100). Inrecent years, not only has it been receiving increasingattention and interest but it has also been used fairlyextensively to produce commercial tonnages of pulp.The major part of this use and interest has centeredaround the ammonium bisulphite process.

To aid those who are interested in the literature ofthis particular field, references have been collected an dclassified for the period 1900 to June, 1953. In classi-fying these references, an attempt has been made toanticipate the interests of both the operational and tech-nical approaches to the subject. No attempt has beenmade to review the material critically. Referencenumbers below 100 are for technical papers and thoseabove 100 are for patents.

COOKING PROCESSES

Kon Process. Wood is heated with ammoniumhydroxide and this treatment is followed by treatmentwith a mineral acid (or vice versa ) (101); a furtherpatent 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 thesaponification of casein to obtain a product which undercertain conditions of pressure and temperature evolvesnascent ammonia which can be used for cooking fibrousmaterials. Merits and demerits are discussed in (8 ,29).

Billwiller. A broad patented process making use ofsuch cooking chemicals as ammonia, sodium carbonate,hydrogen sulphide, etc., with the emphasis on the use ofcatalysts and of a pretreatment using these chemicalsfollowed by known cooking processes (i.e., prior to 1919)(108). For the use of ammonium hydroxide specifi-cally, see (111). Discussion of. merits (12) and general

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 long-leaf pine) followed by the bisulphite (57). Commentson this study (65); others (7, 10, 11, 20, 35, 38).General reviews covering the process are (17, 34, 38,85).

bases including ammonia (63); an industrial review ofthe sulphite (acid) process including evaporation ofliquors (ammonium included) (79); comparison of thevarious sulphite pulping methods from the point ofview of the spent liquors (71).Evaporation


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Miscellaneous Cooking(I) Gaseous Cooking. Sammet and Merrill treatfibrous materials with gaseous ammonia and sulphurdioxide and steam (103); a gaseous pretreatment lab-

oratory trial (16).(II) Using ammonia and steam o

ammonium sulfite

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