US3393122A - Pretreatment of green wood with reducing agent prior to storage - Google Patents

Pretreatment of green wood with reducing agent prior to storage Download PDF

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Publication number
US3393122A
US3393122A US372368A US37236864A US3393122A US 3393122 A US3393122 A US 3393122A US 372368 A US372368 A US 372368A US 37236864 A US37236864 A US 37236864A US 3393122 A US3393122 A US 3393122A
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United States
Prior art keywords
wood
chips
brightness
pulp
sulfur dioxide
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Expired - Lifetime
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US372368A
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English (en)
Inventor
John L Marshall
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Georgia Pacific LLC
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Georgia Pacific LLC
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Publication date
Application filed by Georgia Pacific LLC filed Critical Georgia Pacific LLC
Priority to US372368A priority Critical patent/US3393122A/en
Priority to NO158276A priority patent/NO124168B/no
Priority to SE7187/65A priority patent/SE322684B/xx
Priority to FI651324A priority patent/FI45999C/fi
Priority to JP40032500A priority patent/JPS498801B1/ja
Application granted granted Critical
Publication of US3393122A publication Critical patent/US3393122A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21CPRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C1/00Pretreatment of the finely-divided materials before digesting
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S162/00Paper making and fiber liberation
    • Y10S162/12Seasoning

Definitions

  • This invention pertains to a chemi-mechanical pulping process and more particularly to an improved process whereby a pulp of improved brightness is obtained.
  • the color of chemi-mechanical pulp is also affected by the greeness of the wood from which the pulp is prepared. A darker pulp is obtained with aging of the wood. In all pulping processes, some time delay takes place between the time the tree is cut in the forest, the log hauled to the mill, chipped, and the chips chemically subjected to the pulping reaction. Many times, due to weather conditions and other factors, it is necessary to store logs or the wood after it is chipped for a considerable length of time. It may be months before the product is subjected to pulping. As a result, the pulp obtained is relatively dark and must be bleached to improve the brightness to the extent that the pulp is acceptable for many applications. At times, even extensive bleaching will not produce an acceptable product and the addition of chemical pulp must be made to obtain the necessary brightness.
  • a further object is to provide a method of brightening the pulp obtained in a sulfite chemi-mechanical pulping process.
  • a further object is to provide a process for improving brightness of chemi-mechanical pulp obtained from stored or aged wood.
  • the above and other objects are obtained according to this invention which comprises contacting green wood which is to be used in the chemi-mechanical pulping 3,393,122 Patented July 16, 1968 process with a reducing agent selected from the group consisting of sulfur dioxide, sulfites, hydrosulfites, borohydrides and ascorbic acid to sufficiently impregnate the green wood with the reducing agent to inhibit the darkening of the wood upon aging.
  • a reducing agent selected from the group consisting of sulfur dioxide, sulfites, hydrosulfites, borohydrides and ascorbic acid to sufficiently impregnate the green wood with the reducing agent to inhibit the darkening of the wood upon aging.
  • the wood may be stored for considerable lengths of time without obtaining a darker pulp due to the aging of the wood.
  • the brightness of pulp obtained from wood from a freshly cut tree so treated is somewhat improved over the brightness of the pulp produced from the untreated wood pulped immediately.
  • a further improvement in brightness may be obtained by bleaching after pulping.
  • the extent of this improvement is about the same as that obtained by bleaching pulp from untreated, aged chips.
  • the improvement in brightness obtained by the pretreatment of the wood to inhibit the darkening due to the aging is additive to the improvements in brightness obtained by other treatments to which the pulp may be subjected during and after pulping.
  • the pretreatment of green wood with the reducing agent inhibits certain reactions between particular constituents in the wood which take place upon aging, resulting in the darkening.
  • the constituents formed by aging of the wood are probably dissolved in the chemical pulping processes, since the aging of the wood has no appreciable effect on the color of the pulp obtained.
  • the mild digestion employed in the process possibly does not remove these constituents which remain to darken the pulp.
  • the improvement in brightness is obtained by the pretreatment in preventing the formation of these darkening products.
  • the rate of darkening or loss of brightness of the pulp resulting from the aging of the wood is affected somewhat by the moisture content or dryness of the aging wood but is mainly dependent upon the amount of surface of the wood exposed to the atmosphere. For example, a darker pulp will be obtained upon aging of wood in log form but the rate of darkening is gradual compared to the darkening obtained from wood aged in particulate form where a large surface area is exposed. Eventually, the brightness of the pulp obtained from the wood aged as a log will be about the same as that obtained from wood aged in chip form. For example, hardwood chips, when exposed to the atmosphere, will age sufiiciently in four hours to result in a brightness loss in the resultant pulp of about one-half percent unit.
  • the chips may darken at a rate such that the pulp produced will lose about one percent unit per day until about 70 to 80% of the total darkening is obtained. Substantially all of the darkening due to aging will be completed in one to three weeks. With the wood in log form, it may equire three to four months to attain 75% of the total darkening and possibly six months before substantially all of the darkening is obtained. The presence of moisture somewhat decreases the rate of darkening. However, wood or chips will darken even though stored in water.
  • green wood means wood which has been cut or chemically barked while standing within six months and which has not been exposed to drying such as in a kiln, or otherwise so that the wood at least contains a portion of the original moisture of the tree above the equilibrium moisture content.
  • brightness means the color rating of the pulp as determined and expressed according to TAPPI Standard T-217.
  • wood while in a green state, must be treated with the reducing agent 3 to inhibit the darkening by possibly reacting the reducing agent with particular constituents in the wood.
  • Any of the various known methods of treating wood may be used as long as the wood is impregnated and contacted with the reducing agent. Logs may be treated as such. However, in reducing the wood to a particulate form, the impregnation and contact of the reducing agent may be more effectively obtained. Generally, it is preferred to treat the wood just after it has been chipped or reduced to particulate form.
  • the wood may be treated with the reducing agent in gaseous or liquid state.
  • the agent When the agent is in gaseous state, the wood can be contacted with an atmosphere containing the particular agent.
  • it may be desirable to treat the chips by maintaining an atmosphere containing the desired gas in the storage bins until the chips are processed. At other times, it may be more convenient to wash the chips with a solution containing the desired constituents. Generally, after the chips are washed with the solution, they are drained and stored. A sufiicient amount of the solution is retained by the chips to impregnate them and to inhibit the darkening upon storage.
  • solutions to saturation and atmosphere containing 100% of the reducing agent may be used, generally, the treatment of the wood with the agent is carried out with relatively dilute concentrations of the agent. Solutions containing more than 10% of the reagent are seldom employed. Usually, the concentration of the solution is maintained in the range of .1 to 4% and at times may be less than .0l%. Likewise, for a gaseous reagent, the concentration of the reagent over 10 volume percent is seldom used. Usually, an atmosphere containing less than 1% is employed. The wood is contacted with the reducing agent, in the relatively dilute concentration, until a substantially uniform impregnation of not more than 0.5 weight percent of the chemical, based on dry wood, is obtained throughout. Generally, ambient temperature and pressure are employed, especially for the more reactive agents.
  • chips can be overtreated, especially at high concentrations and elevated temperatures and pressures.
  • the improvement in the brightness of the resulting pulp obtained increases progressively with the time that the wood is subjected to the reducing agent until a maximum brightness is obtained.
  • Further contact or reaction of the wood with the reducing agent generally results in decreasing the brightness of the pulp.
  • the decrease in the brightness by overtreatment, for example, with sulfur dioxide may reach a point that no advantage is obtained by the pretreatment.
  • the preferred operation is to treat the chips with the reactive reducing agents for a time which is within 10% of the time required to obtain the maximum brightness in the final pulp.
  • the contact time to obtain the optimum brightness varies with the concentration as well as conditions of temperature and pressure.
  • concentration in a sulfur dioxide-containing atmosphere which contains from .001 to about 0.1% sulfur dioxide, the wood or chips may be stored at ambient temperature indefinitely without overtreatment.
  • an atmosphere containing about 1% sufur dioxide an optimum brightness may be obtained after about 30 to 60 hours of treatment and then the brightness will gradually decrease with additional treatment, while with a 10% S atmosphere, the maximum brightness may be obtained in about 5 to hours.
  • the optimum contact time is less and the rate of decrease in brightness due to overtreatment is greater.
  • the wood under conditions such as to impregnate the wood substantially uniformly without impregnating any substantial portion of the wood with the reducing agent, for example, S0 or the chemical equivalent thereof, in an amount in excess of 0.5 weight percent, based upon the dry wood, for any appreciable length of time.
  • the reducing agent for example, S0 or the chemical equivalent thereof
  • the wood is treated with a larger amount of the agent, generally the optimum brightness is not obtained and if 0.5% is exceeded no improvement in the final brightness may be obtained.
  • Solutions of sulfur dioxide containing from about 0.1 weight perecnt to saturation of S0 as well as solutions of sulfite and bisulfite salts of metals such as alkali metals and alkaline earth metals and NH may be conveniently used for washing the chips.
  • other sulfite compounds which dissolve or decompose to form sulfite ions may be employed, such as zinc or sodium hydrosulfite, which may react as is or decompose to form sulfur dioxide.
  • the chips are often treated by contacting the chips with an atmosphere containing sulfur dioxide. Generally, after chipping a log, the chips are stored until they are used in enclosed storage bins and thus may be easily subjected to an atmosphere containing sulfur dioxide.
  • the point of maximum improvement in brightness may, at times, be determined by observing the conditions of the wood chips after treatment but prior to pulping.
  • the chips With continued treatment, the chips will progressively lighten and reach a point of maxi-mum brightnes above which very little improvement is obtained with additional treatment.
  • This improvement in the chip may be easily noted by mechanically defibering the pretreated chip prior to contacting the chip with the pulping solution and determining the brightness of the groundwood.
  • the effect of the brightness of the groundwood pulp thus obtained may not necessarily correspond to the brightness of the pulp obtained after the sulfite solution pulping, the point at which the maximum brightness of the groundwood is first obtained is generally close to the contact time at which the optimum brightness is obtained for sulfite chemi-rnechanical pulp.
  • the final brightness and the extent of improvement obtained by the pretreatment of the green wood with the reducing agent will depend upon the conditions employed in the chemi-mechanical pulping process.
  • the wood chips are impregnated with a sulfite solution having a pH in the range of 4.5 to 9.5, and subjected to only a mild digestion in order to obtain a high yield of pulp.
  • a pulp of optimum brightness is generally obtained when the impregnation or digestion liquor employed has a pH in the range of 6.0 to 7.5.
  • a darker pulp is obtained with liquor of higher pH, even though the improvement in brightness obtained by the pretreatment may be greater.
  • EXAMPLE I A red alder log which had been cut two months previous was chipped and a portion of the chips treated prior to storage. One portion of the fresh chips was washed for about one minute with a sulfurous acid solution at a pH of 1.75, allowed to drain, placed in a plastic bag, and stored. A second portion was washed with a sodium sulfite-sodium bisulfite solution at a pH of 6.5 and a concentration of about 0.5 weight percent expressed as S A third portion of chips was placed in a plastic bag without any treatment.
  • the chips were pulped by a neutral sulfite chemi-rnechanical process to a yield of approximately 90%.
  • the chips were steamed for 5 minutes at atmospheric pressure and impregnated with a sodium sulfite solution at a pH of 6.5 under a hydrostatic pressure of 135 p.s.i. for one hour and the excess liquor drained off.
  • the impregnated chips were subjected to a mild digestion by heating with steam at sufficient pressure to obtain a temperature of 150 C. for about minutes.
  • the chips were mechanically defibered, washed, and the brightness of the pulp determined according to TAPPI Standard T-2l7. Both of the samples which had been pretreated had a brightness of 75%.
  • the wood chips which were stored in a plastic bag with no pretreatment had a brightness of 70.3%.
  • EXAMPLE II To illustrate the improvement in brightness obtained by treating the chips with sulfur dioxide gas and also the effect of overtreatrnent, fresh chips from a red alder log, cut one month before chipping, were treated with sulfur dioxide under different conditions. A portion of the chips was placed in a plastic bag and the chips treated by passing sulfur dioxide gas into the bag while the chips were agitated. The bag was then sealed and stored at room temperature for 70 hours. A second batch of chips was placed in a container and continuously subjected, for a period of 68 hours, to a gas stream containing 16 to 18% sulfur dioxide. The treated chips, as Well as a batch of chips which had been stored for 70 hours without being treated, were pulped in a manner similar to that described in Example I to obtain a yield of approximately 90%.
  • the brightness of the pulp obtained from chips which had been purged with sulfur dioxide gas was 77.5% while the brightness of the pulp from chips which had been continuously subjected to the sulfur dioxide stream for 68 hours was 62%. Chips which were stored without any pretreatment had a brightness of 74.7%.
  • the treated chips and a batch of untreated chips which were stored in a plastic bag for 66 hours, were pulped in a manner similar to that above to obtain a yield of approximately 90%.
  • the brightness of the pulp obtained was 76.9% for chips treated with the gas stream containing 0.01% of sulfur dioxide, 76.4% for the chips subjected to the 1% sulfur dioxide gas stream, and 73.1% for the untreated chips.
  • EXAMPLE III A series of batches of fresh alder chips, from a log cut about three months before chipping, was treated with various reducing agents prior to storing and pulping.
  • the chips were washed with a solution of the reducing agent by dumping the chips into the solution and agitating to thoroughly wet the chips. The chips were then placed on a screen and allowed to drain, packed in plastic bags and stored 48 hours.
  • the brightness of the pulps obtained is shown in the table below.
  • EXAMPLE VI Various wood species were treated and the improvement in brightness of the pulp obtained was determined. Green logs of the species were chipped and the fresh chips treated by washing with a sulfurous acid solution having a concentration of 1.0%, expressed as S0 until about 0.2 weight percent S0 based on the dry wood, was retained by the chips. The treated chips and batches of untreated chips were then placed in plastic bags and stored for 42 hours. The chips were pulped in a manner similar to that described in Example I to obtain a yield of The brightness of the pulps obtained is shown below: 1
  • the step to improve the brightness of the pulp which comprises contacting the green wood chips prior to substantial darkening of the surface of the chips with sulfite ions, said chips being contacted with the sulfite ions under conditions of time and concentration to pretreat the chips without impregnating the wood with sulfite ions, expressed as S0 of more than 0.5% of the weight of the wood in a dry state to inhibit the darkening of the chips.
  • green wood is selected from the group consisting of alder, birch, maple, beech, spruce and mixtures thereof.
  • the process for the preparation of high yield pulp of improved brightness from green wood which comprises chipping the wood to obtain the wood in particulate form, immediately washing the chips with a sulfite solution at ambient temperature and pressure, storing the so-treated chips, and pulping the so-treated chips in from four hours to 30 days with a neutral sulfite solution at a pH in the range of 6 to 7.5 to obtain a yield of pulp of at least 16.
  • a process according to claim 15 wherein the chips are contacted at ambient temperature with an aqueous sulfur dioxide solution containing from .1 weight percent to saturation of sulfur dioxide until the chips are impregnated with from 0.005 to 0:15 weight percent of sulfur dioxide, based upon the weight of the wood in a dry state.

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  • Chemical And Physical Treatments For Wood And The Like (AREA)
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US372368A 1964-06-03 1964-06-03 Pretreatment of green wood with reducing agent prior to storage Expired - Lifetime US3393122A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US372368A US3393122A (en) 1964-06-03 1964-06-03 Pretreatment of green wood with reducing agent prior to storage
NO158276A NO124168B (enrdf_load_html_response) 1964-06-03 1965-05-29
SE7187/65A SE322684B (enrdf_load_html_response) 1964-06-03 1965-06-02
FI651324A FI45999C (fi) 1964-06-03 1965-06-03 Menetelmä tuoreen puun käsittelemiseksi kemiallis-mekaanisessa sulfiit timassamenetelmässä.
JP40032500A JPS498801B1 (enrdf_load_html_response) 1964-06-03 1965-06-03

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US372368A US3393122A (en) 1964-06-03 1964-06-03 Pretreatment of green wood with reducing agent prior to storage

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JP (1) JPS498801B1 (enrdf_load_html_response)
FI (1) FI45999C (enrdf_load_html_response)
NO (1) NO124168B (enrdf_load_html_response)
SE (1) SE322684B (enrdf_load_html_response)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3808037A (en) * 1971-05-12 1974-04-30 Scm Canada Ltd Anti-stain treatment for water-repellent coated lumber in transit
US4211605A (en) * 1978-08-03 1980-07-08 Canadian International Paper Company High yield chemimechanical pulping processes
FR2539155A1 (fr) * 1983-01-12 1984-07-13 Billeruds Ab Traitement de copeaux de bois
US4788790A (en) * 1986-06-06 1988-12-06 Zeager Charles B Method of making a dark, uniformly-colored, hardwood mulch
US5035772A (en) * 1987-02-27 1991-07-30 Mooch Domsjo Ab Method for treating bleached lignin containing cellulose pulp by reducing α-carbonyl and γ-carbonyl groups and converting short-wave quanta to long-wave light quanta
WO1992009745A1 (en) * 1990-12-03 1992-06-11 Mo Och Domsjö Aktiebolag Paper and a method of paper manufacture
US5169496A (en) * 1991-04-23 1992-12-08 International Paper Company Method of producing multi-ply paper and board products exhibiting increased stiffness
US5460697A (en) * 1992-10-09 1995-10-24 Wisconsin Alumni Research Foundation Method of pulping wood chips with a fungi using sulfite salt-treated wood chips

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1169597A (en) * 1912-12-14 1916-01-25 Berlin Mills Company Method of preparing wood-pulp.
US1904894A (en) * 1930-05-27 1933-04-18 Westad Daniel Process and apparatus for the manufacture of cellulose
GB829506A (en) * 1956-11-05 1960-03-02 Eugene Gilbert Voiret Improvements in the manufacture of wood putp

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1169597A (en) * 1912-12-14 1916-01-25 Berlin Mills Company Method of preparing wood-pulp.
US1904894A (en) * 1930-05-27 1933-04-18 Westad Daniel Process and apparatus for the manufacture of cellulose
GB829506A (en) * 1956-11-05 1960-03-02 Eugene Gilbert Voiret Improvements in the manufacture of wood putp

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3808037A (en) * 1971-05-12 1974-04-30 Scm Canada Ltd Anti-stain treatment for water-repellent coated lumber in transit
US4211605A (en) * 1978-08-03 1980-07-08 Canadian International Paper Company High yield chemimechanical pulping processes
FR2539155A1 (fr) * 1983-01-12 1984-07-13 Billeruds Ab Traitement de copeaux de bois
US4788790A (en) * 1986-06-06 1988-12-06 Zeager Charles B Method of making a dark, uniformly-colored, hardwood mulch
US5035772A (en) * 1987-02-27 1991-07-30 Mooch Domsjo Ab Method for treating bleached lignin containing cellulose pulp by reducing α-carbonyl and γ-carbonyl groups and converting short-wave quanta to long-wave light quanta
WO1992009745A1 (en) * 1990-12-03 1992-06-11 Mo Och Domsjö Aktiebolag Paper and a method of paper manufacture
US5368689A (en) * 1990-12-03 1994-11-29 Mo Och Domsjo Aktiebolag Paper and a method of paper manufacture
US5169496A (en) * 1991-04-23 1992-12-08 International Paper Company Method of producing multi-ply paper and board products exhibiting increased stiffness
US5460697A (en) * 1992-10-09 1995-10-24 Wisconsin Alumni Research Foundation Method of pulping wood chips with a fungi using sulfite salt-treated wood chips

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Publication number Publication date
JPS498801B1 (enrdf_load_html_response) 1974-02-28
SE322684B (enrdf_load_html_response) 1970-04-13
FI45999C (fi) 1972-11-10
NO124168B (enrdf_load_html_response) 1972-03-13
FI45999B (enrdf_load_html_response) 1972-07-31

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