US20070240837A1 - Hardwood alkaline pulping processes and systems - Google Patents

Hardwood alkaline pulping processes and systems Download PDF

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Publication number
US20070240837A1
US20070240837A1 US11/709,278 US70927807A US2007240837A1 US 20070240837 A1 US20070240837 A1 US 20070240837A1 US 70927807 A US70927807 A US 70927807A US 2007240837 A1 US2007240837 A1 US 2007240837A1
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United States
Prior art keywords
lignin
cooking
cooking stage
slurry
hardwood material
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Abandoned
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US11/709,278
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English (en)
Inventor
Nam Hee Shin
C. Bertil Stromberg
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Andritz Inc
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Andritz Inc
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Priority to US11/709,278 priority Critical patent/US20070240837A1/en
Application filed by Andritz Inc filed Critical Andritz Inc
Priority to AU2007200969A priority patent/AU2007200969B2/en
Priority to CA002581993A priority patent/CA2581993A1/en
Priority to PT103701A priority patent/PT103701B/pt
Priority to ES200700816A priority patent/ES2319035B1/es
Assigned to ANDRITZ INC. reassignment ANDRITZ INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SHIN, NAM HEE, STROMBERG, C. BERTIL
Priority to JP2007096441A priority patent/JP5101917B2/ja
Priority to CL200701000A priority patent/CL2007001000A1/es
Priority to UY30266A priority patent/UY30266A1/es
Priority to FI20070280A priority patent/FI20070280A/fi
Priority to RU2007113735/12A priority patent/RU2414555C2/ru
Priority to BRPI0701613-1A priority patent/BRPI0701613A/pt
Priority to SE0700888A priority patent/SE531540C2/sv
Priority to CN2007100981106A priority patent/CN101054777B/zh
Publication of US20070240837A1 publication Critical patent/US20070240837A1/en
Priority to US13/572,403 priority patent/US20120305209A1/en
Abandoned legal-status Critical Current

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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/02—Pulping cellulose-containing materials with inorganic bases or alkaline reacting compounds, e.g. sulfate processes
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/02—Pulping cellulose-containing materials with inorganic bases or alkaline reacting compounds, e.g. sulfate processes
    • D21C3/022—Pulping cellulose-containing materials with inorganic bases or alkaline reacting compounds, e.g. sulfate processes in presence of S-containing compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/22—Other features of pulping processes
    • D21C3/24—Continuous processes
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/22—Other features of pulping processes
    • D21C3/26—Multistage processes
    • D21C3/266—Multistage processes the same pulping agent being used in all stages
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C1/00—Pretreatment of the finely-divided materials before digesting
    • D21C1/06—Pretreatment of the finely-divided materials before digesting with alkaline reacting compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/22—Other features of pulping processes
    • D21C3/222—Use of compounds accelerating the pulping processes
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/22—Other features of pulping processes
    • D21C3/26—Multistage processes

Definitions

  • the present invention relates generally to the field of chemical treatments of comminuted cellulosic fibrous material.
  • the present invention relates to processes and apparatus for the alkaline pulping of comminuted hardwoods.
  • Chemical cooking of hardwoods can typically result in greater pulp rejects as compared to pulp obtained from the chemical cooking of softwoods at Kappa numbers of 17 and greater.
  • the present applicants have discovered that the middle lamella in hardwoods have substantial amounts of guaiacyl lignin (g-lignin) on a cellular level in the middle lamella as compared to the presence of syringyl lignin (s-lignin).
  • g-lignin guaiacyl lignin
  • s-lignin guaiacyl lignin
  • the lignin in the middle lamella of hardwoods is predominantly g-lignin.
  • the middle lamella of softwood cells will typically be substantially entirely comprised of g-lignin.
  • methods and systems for continuously producing chemical cellulose pulp from a slurry of comminuted hardwood material by subjecting the slurry of comminuted hardwood material to a first cooking stage under conditions sufficient to reduce syringyl lignin (s-lignin) content in the hardwood material as compared to guaiacyl lignin (g-lignin) content therein, and thereafter subjecting the slurry of comminuted hardwood material to a second cooking stage under conditions sufficient to reduce the g-lignin content remaining therein after the first cooking stage.
  • s-lignin syringyl lignin
  • g-lignin guaiacyl lignin
  • the first stage of cooking of the hardwood material (that is the treatment stage after pretreatment or impregnation) is practiced so as to subject the hardwood material to a temperature of between about 120° C. to about 170° C. at about 2 to about 10% effective alkaline charge as (EA) NaOH on wood and/or so that the Kappa number for the cooked hardwood material which exits the first cooking stage is between about 30 to about 100.
  • EA effective alkaline charge
  • the first cooking stage is conducted under a low sulfidity condition of less than about 20% sulfidity.
  • a low sulfidity condition of the first cooking stage may be performed, if necessary, by adding a sufficient amount of preferably anthroquinone and/or polysulfide.
  • the second cooking stage is practiced so as to subject the slurry of hardwood material to a temperature of between about 130° C. to about 180° C. at about 2 to about 10% effective alkaline charge as (EA) NaOH on wood and/or so that the Kappa number for the cooked hardwood material which exits the second cooking stage is between about 15 to about 30.
  • EA effective alkaline charge
  • the second cooking stage be conducted under a higher sulfidity condition of greater than about 20% sulfidity with or without the addition of anthraquinone and/or polysulfide.
  • the comminuted hardwood material may optionally be pretreated. If employed, the pretreatment occurs prior to the first cooking zone at about 20 to about 70% of the total effective alkaline charge as (EA) NaOH on wood at a temperature between about 80 to about 120° C.
  • EA effective alkaline charge
  • FIG. 1 is a schematic presentation of exemplary apparatus for practicing the method according to the present invention, and comprising an exemplary system according to the present invention
  • FIG. 2 is a graph of the percent lignin from the original lignin of the cellulose material remaining at each of the sample points during a hardwood cook;
  • FIG. 3 is a graph representing the ratio of s-lignin to g-lignin at various stages of a hardwood cook.
  • FIG. 1 illustrates one preferred embodiment of the present invention.
  • FIG. 1 illustrates a comminuted cellulosic fibrous material treatment system 10 consisting essentially of or comprising a continuous digester 11 having a continuous digester feed system 12 .
  • Feed system 12 may be a LO-LEVEL® feed system or a TURBOFEED® system both as sold by Andritz Inc. but any conventional feed system for introducing, steaming, and slurrying comminuted cellulosic fibrous material may be used; and/or one or more separate impregnation vessels may be used; and/or unconventional systems, such as those including equipment and/or a chip bin in the wood yard with pumping to the digester.
  • a plurality of impregnation vessels may be used, with slurry pumped from a particular vessel once impregnation with, or without, cooking additive is complete (or will complete during pumping).
  • Comminuted cellulosic fibrous material for example, in the form of hardwood chips 13 , are introduced to feed system 12 , as described in U.S. Pat. Nos. 5,763,075; 6,106,668; 6,325,890; 6,551,462; 6,336,993; 6,841,042 (the entire content of each patent being expressly incorporated hereinto by reference), and marketed by Andritz Inc. under the trademark TURBOFEED®; or a feed system as described in U.S. Pat. Nos. 5,476,572; 5,700,355; 5,968,314 (the entire content of each patent being expressly incorporated hereinto by reference), and marketed by Andritz Inc.
  • LO-LEVEL® which may include forwarding the chips to steam treatment in a vessel 14 , which is preferably a vessel as described in U.S. Pat. Nos. 5,500,083; 5,617,975; 5,628,873; 4,958,741; and 5,700,355 (the entire content of each patent being expressly incorporated hereinto by reference), and marketed by Andritz Inc. under the trademark DIAMONDBACK®, though other types of steaming vessels may be used. From the vessel the chips pass through equipment such as a metering device connected to a conduit, which is preferably a Chip Tube provided by Andritz Inc. The slurry of chips and liquid is fed to the impregnation vessel (if used) or to the digester 11 via a pressurizing means.
  • a vessel 14 which is preferably a vessel as described in U.S. Pat. Nos. 5,500,083; 5,617,975; 5,628,873; 4,958,741; and 5,700,355 (the entire content
  • the slurry pressurized typically, to a pressure of between about 5 and 15 bar and propels the slurry via conduit 21 to the top of the continuous digester 11 .
  • Excess liquor contained in the slurry is removed from the slurry at the inlet of the digester 11 by a separating device 22 , typically a conventional Top Separator, and the excess liquid is removed and returned to feed system 12 via conduit 23 .
  • the slurry of hardwood material may be pretreated at an alkaline charge of between about 20 to about 70% of total effective alkaline (EA) NaOH charge on wood at a temperature between about 80 to about 120° C., preferably between about 100 to about 110° C.
  • EA total effective alkaline
  • Feed system 12 also typically includes conventional non-illustrated devices such as in-line drainer, level tank, and make-up liquor pump.
  • Cooking liquor for example, kraft white liquor (WL) is typically provided to the level tank (not shown) as is conventional.
  • the pretreated hardwood material (which may, but not necessarily, have been treated in an impregnation vessel) fed via line 21 is subjected to a first cooking stage in digester 11 .
  • the pretreatment of the hardwood material as described above is not absolutely necessary as the hardwood material may be fed directly into the digester 11 .
  • the first cook within digester 11 is conducted under low sulfidity conditions (i.e., 0-20% sulfidity) using a beneficial additive such as anthroquinone (AQ) and/or polysulfide.
  • the first cooking stage in digester 11 is conducted at temperatures of between about 120 to about 170° C. using an alkaline charge of between about 2 to about 10% effective alkaline (EA) NaOH charge on wood.
  • the cooked hardwood material exits digester 11 via line 30 having a Kappa number of between about 30 to about 100 (preferably between about 40 to about 60).
  • the hardwood material after the first cooking stage in digester 11 has a higher proportion of g-lignin relative to s-lignin than at the beginning of the first cooking stage.
  • High concentration of s-lignin in surrounding liquor may interfere with the dissolution of g-lignin remaining in the hardwood material.
  • the hardwood material may optionally be transferred to a wash vessel 32 via line 30 and subjected to wash conditions with a wash liquor introduced via line 34 .
  • Spent wash liquor is removed from the wash vessel 32 via line 36 . Since the wash stage within wash vessel 32 reduces the s-lignin in surrounding liquor, any cooking additives which could later be used would not be detrimentally consumed by the already dissolved s-lignin in the surrounding liquor.
  • the washed pulp which exits the optional wash vessel 32 via line 38 is directed to a digester 40 where a second cooking stage is conducted so as to further breakdown and reduce the g-lignin content in the hardwood material.
  • Breakdown of g-lignin can be accomplished by use of high sulfidity cooking liquor (i.e., greater than about 20% sulfidity, and preferably between about 25 to about 40% sulfidity) with or without AQ and/or polysulfide. (See for example U.S. Pat. No. 6,576,084, the entire content is expressly incorporated hereinto by reference).
  • Other cooking chemicals that work well under cooking conditions, such as sulfite could also be used alone or in conjunction with AQ and/or polysulfide as mentioned above.
  • the second cooking stage in digester 40 is conducted at a temperature between about 130 to about 180° C., preferably between about 140 to about 180° C., with an alkali charge of between about 2 to about 10% EA charge on wood (original wood charge) and a Kappa number at the beginning of the second cooking stage of between about 30 to about 100 (preferably between about 40 to about 60). During this phase, it may be advantageous (but not always necessary) to increase the temperature to above that of the first cooking stage.
  • the hardwood material be allowed to continue to cook at a temperature of at least about 130°.
  • the Kappa number will preferably be between 15 to 30, more preferably between about 17 to about 30.
  • the hardwood material is divided into two distinct cooking stages.
  • the H-factor achieved at the end of the second cooking stage is as least 50% of the total H-factor that is achieved for the entire cook. Stated another way, the H-factor achieved through the first cooking stage is less than 50% of the H-factor achieved for the entire cook (i.e., at the end of the second cooking stage).
  • the cooking stages, and washing stage if used are preformed in a single digester vessel. If a single vessel is used the same operating parameters for each stage as described would be used and end of stage would not require intermediate transfer of material to multiple vessels.
  • the first and second cooking stages conducted in digesters 11 and 40 , respectively, or in a single digester vessel, is preferably conducted in accordance with one or more of the processes described more fully in U.S. Pat. Nos. 5,489,363; 5,536,366; 5,547,012; 5,575,890; 5,620,562; and 5,662,775 (the entire contents of each such patent being expressly incorporated hereinto by reference).
  • the processes and apparatus disclosed in these patents are marketed under the trademark LO-SOLIDS® Cooking by Andritz Inc. of Glens Falls, N.Y.
  • the processes and apparatus of the present invention produce a pulp low in HexA content as a result of the relatively high temperature of the new treatment and/or cooking in the second cooking stage.
  • This low HexA pulp favors oxygen delignification conditions which in turn provides for a low Kappa number pulp to a subsequent bleaching process.
  • the low Kappa number pulp may therefore be bleached using less chemicals thereby resulting in lower effluent loading.
  • a hardwood cooking cycle was performed using a total EA (effective alkaline as NaOH) charge of 18% introduced during the impregnation, first cook and second cook stages. The following conditions were used during each of the stages:
  • the high temperature in the second stage of the cook gave lower Kappa number and at least 30% lower reject rate than the set of cooking conditions using 140° C. cooking temperature in both cook stages under the same alkali charge and the same H-factor.
  • a hardwood cooking cycle was performed using a total EA (effective alkaline as NaOH) charge of 17.5% introduced during the impregnation, first (or upper) cook and second (or lower) cook sequences. The following conditions were used during each of the cook sequences:
  • FIG. 2 is a plot of the percent of lignin from the original cellulosic material remaining at each of the sample points. At the beginning of impregnation, 100% of the lignin is present, but by the end of the 2 nd (lower) cook zone only about 3% of the lignin remains. As a general rule, wood chips prior to treatment contain about 24% lignin which means from the data of FIG. 2 the amount of lignin is only about 0.72% of the wood chips and thus any analysis of s-lignin and g-lignin content would not be accurate.
  • FIG. 3 present data that shows the change in the ratio of s-lignin to g-lignin as the cook described above progressed.
  • the first ratio of 2.74 is the initial ratio before the addition of any liquor or any treatment.
  • the second ratio of 2.87 is at end of impregnation.
  • the third and fourth ratios of 2.64 and 2.54 are respectively at the middle of the first cook stage and at the end of the first cook stage.
  • the fifth and final ratio of 2.47 is at the middle of the second cook stage.
  • the data of FIG. 3 thus suggests that the s-lignin is being broken down or dissolved at a faster rate than that of the g-lignin.
  • the g-lignin content remains present on a cellular level which requires a different set of conditions to cause it to break apart and be destroyed or dissolved.
  • operating conditions in the digester must change in the later stages of the cook.
  • the later stages of the cook require a higher temperature as compared to the early stages to ensure that the g-lignin is destroyed and to improve the yield (thereby reducing the rejects) and physical properties of the pulp.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
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US11/709,278 2006-04-13 2007-02-22 Hardwood alkaline pulping processes and systems Abandoned US20070240837A1 (en)

Priority Applications (14)

Application Number Priority Date Filing Date Title
US11/709,278 US20070240837A1 (en) 2006-04-13 2007-02-22 Hardwood alkaline pulping processes and systems
AU2007200969A AU2007200969B2 (en) 2006-04-13 2007-03-06 Hardwood Alkaline Pulping Processes and Systems
CA002581993A CA2581993A1 (en) 2006-04-13 2007-03-08 Hardwood alkaline pulping processes and systems
PT103701A PT103701B (pt) 2006-04-13 2007-03-26 Sistemas e processos de produção alcalina de pasta de madeira dura
ES200700816A ES2319035B1 (es) 2006-04-13 2007-03-28 Sistemas y procesos de formacion de pulpa alcalina de maderas duras.
JP2007096441A JP5101917B2 (ja) 2006-04-13 2007-04-02 広葉樹材からアルカリパルプを製造する方法および装置
UY30266A UY30266A1 (es) 2006-04-13 2007-04-10 Procesos y sistemas de fabricacion de pulpa alcalina de madera de frondosas
CL200701000A CL2007001000A1 (es) 2006-04-13 2007-04-10 Metodo para la produccion continua de pulpa quimica de celulosa a partir de una pasta de material de madera dur< triturada que comprende someter la pasta a coccion bajo condiciones para reducir el contenido de siringil lignina y luego someter a cocci
SE0700888A SE531540C2 (sv) 2006-04-13 2007-04-12 Alkalisk massaberedningsprocess och -system för lövved
FI20070280A FI20070280A (fi) 2006-04-13 2007-04-12 Menetelmä ja järjestelmä kemiallisen massan jatkuvatoimiseksi tuottamiseksi
RU2007113735/12A RU2414555C2 (ru) 2006-04-13 2007-04-12 Способ и установка для щелочной варки целлюлозы из древесины твердых пород
BRPI0701613-1A BRPI0701613A (pt) 2006-04-13 2007-04-12 processos e sistemas para reduzir para polpa alcalina madeiras de lei
CN2007100981106A CN101054777B (zh) 2006-04-13 2007-04-13 阔叶木碱法制浆方法及系统
US13/572,403 US20120305209A1 (en) 2006-04-13 2012-08-10 Hardwood alkaline pulping processes and systems

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US79143106P 2006-04-13 2006-04-13
US11/709,278 US20070240837A1 (en) 2006-04-13 2007-02-22 Hardwood alkaline pulping processes and systems

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US13/572,403 Division US20120305209A1 (en) 2006-04-13 2012-08-10 Hardwood alkaline pulping processes and systems

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US20070240837A1 true US20070240837A1 (en) 2007-10-18

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US11/709,278 Abandoned US20070240837A1 (en) 2006-04-13 2007-02-22 Hardwood alkaline pulping processes and systems
US13/572,403 Abandoned US20120305209A1 (en) 2006-04-13 2012-08-10 Hardwood alkaline pulping processes and systems

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US13/572,403 Abandoned US20120305209A1 (en) 2006-04-13 2012-08-10 Hardwood alkaline pulping processes and systems

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US (2) US20070240837A1 (ja)
JP (1) JP5101917B2 (ja)
CN (1) CN101054777B (ja)
AU (1) AU2007200969B2 (ja)
BR (1) BRPI0701613A (ja)
CA (1) CA2581993A1 (ja)
CL (1) CL2007001000A1 (ja)
ES (1) ES2319035B1 (ja)
FI (1) FI20070280A (ja)
PT (1) PT103701B (ja)
RU (1) RU2414555C2 (ja)
SE (1) SE531540C2 (ja)
UY (1) UY30266A1 (ja)
ZA (1) ZA200701944B (ja)

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US20100028966A1 (en) * 2008-07-28 2010-02-04 Jeffrey Blanchard Methods and Compositions for Improving The production Of Products In Microorganisms
US20100035320A1 (en) * 2008-07-28 2010-02-11 Jeffrey Blanchard Methods and compositions for improving the production of products in microorganisms
US20100086981A1 (en) * 2009-06-29 2010-04-08 Qteros, Inc. Compositions and methods for improved saccharification of biomass
US20100136661A1 (en) * 2006-01-27 2010-06-03 Susan Leschine Systems and methods for producing biofuels and related materials
US20110183382A1 (en) * 2009-12-15 2011-07-28 Qteros, Inc. Methods and compositions for producing chemical products from c. phytofermentans
US20110230682A1 (en) * 2010-03-19 2011-09-22 Qteros, Inc. Microorganisms with inactivated lactate dehydrogenase gene (ldh) for chemical production
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WO2013033386A1 (en) * 2011-08-30 2013-03-07 Cargill, Incorporated Pulping processes
US11390990B2 (en) * 2017-10-17 2022-07-19 Auburn University Phenols as additives in kraft pulping

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SE532932C2 (sv) * 2008-03-20 2010-05-11 Metso Fiber Karlstad Ab Matningssystem innefattande parallella pumpar för en kontinuerlig ångfaskokare utan toppseparator
US7867363B2 (en) * 2008-08-27 2011-01-11 Metso Fiber Karlstad Ab Continuous digester system
US8951388B2 (en) * 2011-04-08 2015-02-10 Pec-Tech Engineering And Construction Pte Ltd Method and system for efficient production of dissolving pulp in a kraft mill producing paper grade pulp with a continuous type digester
JP5783453B2 (ja) * 2011-09-21 2015-09-24 川崎化成工業株式会社 パルプ化におけるアントラキノン化合物の添加効果の算定方法
CN103410036B (zh) * 2013-08-15 2015-11-18 齐鲁工业大学 一种阔叶木高得率浆的生产方法
CN103835173B (zh) * 2014-03-17 2015-09-16 昆明理工大学 一种大龙竹预浸渍二乙醇胺-蒽醌蒸煮制浆方法
CN104407098B (zh) * 2014-09-23 2016-04-20 黄伟洪 一种快速评价桦木烧碱蒽醌法制浆工艺的方法
CN105568739B (zh) * 2014-10-15 2017-12-12 亚太森博（山东）浆纸有限公司 一种原色硫酸盐阔叶木浆板及其制备方法
CN105568740B (zh) * 2014-10-15 2017-12-12 亚太森博（山东）浆纸有限公司 一种高强度低白度硫酸盐阔叶木浆板及其制备方法

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AU2007200969B2 (en) 2011-11-03
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PT103701B (pt) 2008-01-28

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