[go: up one dir, main page]

WO2000028135A1 - Traitement de lessive noire - Google Patents

Traitement de lessive noire Download PDF

Info

Publication number
WO2000028135A1
WO2000028135A1 PCT/CA1999/001048 CA9901048W WO0028135A1 WO 2000028135 A1 WO2000028135 A1 WO 2000028135A1 CA 9901048 W CA9901048 W CA 9901048W WO 0028135 A1 WO0028135 A1 WO 0028135A1
Authority
WO
WIPO (PCT)
Prior art keywords
black liquor
hydrocarbon liquid
viscosity
hydrophobic hydrocarbon
liquor
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CA1999/001048
Other languages
English (en)
Inventor
James W. Smith
Zhi-Zhong Liang
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Thor Technology Corp
Original Assignee
Thor Technology Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Thor Technology Corp filed Critical Thor Technology Corp
Priority to AU10239/00A priority Critical patent/AU1023900A/en
Publication of WO2000028135A1 publication Critical patent/WO2000028135A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/005—Lignin
    • 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
    • D21C11/00—Regeneration of pulp liquors or effluent waste waters
    • D21C11/0085—Introduction of auxiliary substances into the regenerating system in order to improve the performance of certain steps of the latter, the presence of these substances being confined to the regeneration cycle
    • D21C11/0092—Substances modifying the evaporation, combustion, or thermal decomposition processes of black liquor

Definitions

  • the present invention relates to the processing of black liquor to reduce black liquor viscosity and achieve high solids content.
  • wood or other cellulosic material is pulped in a white liquor comprising predominantly sodium sulfide and sodium hydroxide to form wood pulp.
  • the wood pulp is separated from the spent pulping liquor and further processed by washing and optionally bleaching.
  • the spent pulping liquor or black liquor is subjected to a recovery and regeneration cycle for forming fresh pulping liquor.
  • a recovery and regeneration cycle for forming fresh pulping liquor.
  • Such procedure generally involves evaporation of the black liquor, smelting the concentrated black liquor, forming green liquor from the smelt by dissolving the solid mass in water and forming white liquor from the green liquor by recausticization.
  • the viscosity and solids content of the black liquor increase. Such increase in viscosity tends to become exponential with solids content at solids content in excess of about 50% by weight. As the viscosity increases, the black liquor becomes more difficult to handle. In general, however, for the same solids content, the higher the temperature of the black liquor, the lower the viscosity. It would be desirable to provide a high solids content concentrated black liquor at lower viscosity and temperature to improve the processability and economics of recovery of the black liquor.
  • the relatively high viscosity of black liquor is believed to be due to the interaction of polymers, particularly hemicellulose and lignin. The hemicelluloses tend to entangle, and both hemicellulose and lignin form agglomerates which are not readily plasticized by water at solids concentrations much in excess of about 50%.
  • lignin agglomerates The formation of lignin agglomerates is believed to be due to four mechanisms, namely hydrogen bonding, stereoregular association, lyophobic bonding and charge transfer bonding. Such association leads to extremely high viscosity of black liquor at solids concentration in the range of 70 to 80%.
  • Black liquor as formed in the Kraft process is a complex colloidal system consisting of water, organic and inorganic sulfur compounds, inorganic sodium salts, primarily in the form of carbonates and sulfides, residual caustic soda, hemicellulose and lignin.
  • the primary lignin fragments have a molecular weight of about 10,000 with a high degree of variation, but the fragments tend to agglomerate or associate with each other, as does the hemicellulose. It is known that shearing black liquor at relatively low shear rates reduces the viscosity reversibly by shear thinning, but the hemicellulose and lignin reassociate, leading to the same high viscosities upon ageing of the processed black liquor for an hour or two. At high shear rates in excess of 25,000 reciprocal seconds, and at solids content in excess of 50% and at temperatures in excess of about 100°C, (U. S. Patent No.
  • Gagnon et al (Pulp and Paper Canada 97: 12, pT428-431, 1996) have disclosed the use of a hydrophilic additive, for example, ethylene glycol, as a replacement for the plasticizing effect of water in strong liquor.
  • the hydrophilic agents are effective, but those available are expensive, and often have relatively low fuel value.
  • Spontak et al (U. S. Patent No. 5,900,112) have disclosed the use of certain salts, preferably isocyanate salts, for reducing black liquor viscosity, but these salts are expensive and have no fuel value, creating an additional load on the recovery boiler.
  • hydrocarbon liquids for example, fuel oil
  • concentrated black liquor of greater than about 50% solids
  • surfactant (s) which may occur naturally in the black liquor or be present in the hydrocarbon liquid
  • the surfactant (s) reducing polymer interactions such as complex formation, re- agglomeration and re-entanglement of the polymers of black liquor.
  • the fuel oil used may be No. 6 Residual (Bunker C) fuel, or asphalt, which can contain relatively high amounts of sulfur.
  • the sulfur presents no problem in the process, since it is captured in the recovery boiler.
  • Another advantage of using such hydrocarbon liquids as disclosed above is their low vapor pressure. Because the price of fuel oil is relatively low, and may depend inversely, at least in part, on its sulfur content, the use of hydrocarbon liquids presents an obvious economic advantage over other additives.
  • the fuel value of the additives disclosed herein can be advantageously used in the production of electrical energy and of steam for the processes encountered in pulp and paper mills.
  • the quantity of hydrophobic hydrocarbon liquid employed is generally about 1 to 50%, preferably about 2 to about 10%.
  • Surfactants which may be used in the present invention may be anionic, preferably sulfonates, such as dodecyl benzene sulfonate.
  • the surfactants may be those found in fresh or recycled lubricating oil.
  • the present invention provides a method of controlling the viscosity of black liquor from a pulping operation by subjecting the black liquor to physical conditions to effect the plasticization of black liquor by the addition of hydrophobic hydrocarbon liquids, with or without the addition of surfactants and under high or low shear blending conditions, whereby the liquor containing the hydrocarbon liquids retains a processable viscosity of under about 10,000 mPa.s at a temperature of about 80°C and significantly lower water content than is otherwise achievable.
  • the reduction in viscosity which is achieved herein permits further processing of the black liquor, whereby the water content of the black liquor can be reduced from, say about 35% to less than about 25%, corresponding to an increase in solids content to at least about 75%.
  • the surfactant (s) may be an anionic surfactant, and/or those contained in lubricating oil, may be added to the black liquor prior to subjecting the black liquor to the process of blending oil or may be added to the hydrocarbon liquid prior to such blending.
  • the invention is particularly concerned with producing black liquor with solids concentration of at least about 75% by blending a suitable hydrocarbon liquid into black liquor in a suitable shear mill, such as a Siefer mill, wherein the initial black liquor concentration is about 40 to about 75%, and a surfactant, if necessary, is added to the black liquor before the blending process.
  • the quantity of surfactant employed may vary, depending on the surfactant chosen and the properties of the black liquor and hydrocarbon liquid processed and is generally from about 0.1 to about 5%.
  • a method for improving the processability of spent pulping liquor (black liquor) and/or reducing the water content of black liquor which comprises blending the black liquor with a quantity of hydrophobic hydrocarbon liquid, thereby producing an emulsion, sufficient to effect a reduction in viscosity of the emulsion over that of the black liquor by at least about 10% at a fixed water content.
  • a method of controlling the viscosity of spent pulping liquor (black liquor) from a pulping operation which comprises blending the spent pulping liquor with a hydrophobic hydrocarbon liquid while removing water from the black liquor to provide a blend and retaining a processable viscosity of less than about 10,000 mPa.s at a temperature of less than about 80°C and significantly lower water content that is otherwise achievable.
  • an emulsion comprising a spent pulping liquor (black liquor) , and sufficient hydrophobic hydrocarbon liquid to effect a reduction of at least about 10% of the viscosity of the black liquor in the emulsion.
  • a blend of spent pulping liquor and hydrophobic hydrocarbon liquid having a solids content of at least about 75%, a moisture content of less than about 25% and viscosity of less than about 10,000 mPa . s at a temperature less than about 80°C.
  • Figure 1 is a graphical representation of viscosity vs. solid content for the experiments described in the Examples below.
  • Example A-2 High shear, 5% #2 fuel oil, 0.5% surfactant
  • Example A sample of the black liquor was blended with the #2 fuel oil under high shear conditions for 45 minutes at 85°C.
  • the viscosity increased with increasing solids content until, after 45 minutes, and at a concentration of 69.9% solid, or a combined oil + solids of 74.4, the viscosity was 5,400 mPa.s, although fluctuating towards higher values.
  • This Example in contrast to Examples C-l and C-2, but in concordance with Example A-l, shows that a readily processable apparently homogeneous blend can be achieved with a significant increase in solids content and decrease in water content.
  • the addition of surfactant appears to have improved the plasticizing effect of the oil additive, yielding a measurably lower viscosity.
  • the present invention provides a novel procedure for processing spent pulping chemicals (black liquor) by blending the said black liquor with a suitable hydrophobic hydrocarbon liquid, such as recycled lubricating oil or fuel oil, which may permit the solid content to be increased and/or the processability of black liquor and/or the efficiency of black liquor evaporation and recovery furnaces to be improved, wherein re-association of degraded macromolecules is inhibited by a hydrocarbon/surfactant combination, said surfactant being naturally present in the black liquor or hydrocarbon liquid or added, as necessary, and said petroleum liquids or hydocarbons act as plasticizers, replacing water and permitting increased solids concentrations.
  • a suitable hydrophobic hydrocarbon liquid such as recycled lubricating oil or fuel oil
  • Residual Fuel or asphalt may contain relatively high proportions of sulfur, which in turn is captured in the recovery boiler where it is converted to a chemical form useful in the pulping process, reducing the need for the addition of make-up sulfur. Modifications are possible within the scope of the invention.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Paper (AREA)

Abstract

On mélange la lessive noire à des liquides hydrocarbonés hydrophobes, en ajoutant ou non des tensioactifs, ce qui donne lieu à une émulsion rapidement décantée et l'on obtient, de ce fait, une émulsion à teneur élevée en matière solides et d'une forte valeur combustible, tout en conservant une viscosité susceptible d'être traitée à des températures relativement basses. Le liquide hydrocarboné (par exemple, du combustible résiduaire N° 6) peut être faiblement volatil et posséder une teneur élevée en soufre sans pour autant avoir des incidences néfastes sur l'environnement, le soufre étant capturé dans une chaudière de récupération, et se révéler des plus utile comme produit de remplacement de soufre d'appoint, essentiel dans le cadre du procédé Kraft.
PCT/CA1999/001048 1998-11-06 1999-11-05 Traitement de lessive noire Ceased WO2000028135A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU10239/00A AU1023900A (en) 1998-11-06 1999-11-05 Black liquor processing

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US10733498P 1998-11-06 1998-11-06
US60/107,334 1998-11-06

Publications (1)

Publication Number Publication Date
WO2000028135A1 true WO2000028135A1 (fr) 2000-05-18

Family

ID=22316104

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CA1999/001048 Ceased WO2000028135A1 (fr) 1998-11-06 1999-11-05 Traitement de lessive noire

Country Status (2)

Country Link
AU (1) AU1023900A (fr)
WO (1) WO2000028135A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6737443B1 (en) * 1998-02-23 2004-05-18 Polyphalt Inc. Lignin based colloidal compositions

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4032473A (en) * 1975-06-04 1977-06-28 Associated Chemists, Inc. Water-based defoamer compositions
EP0194845A2 (fr) * 1985-03-11 1986-09-17 Research Association of Pulp and Paper Technology Procédé pour la concentration d'une liqueur noire
JPS61245391A (ja) * 1985-04-18 1986-10-31 株式会社片山化学工業研究所 紙・パルプ工場におけるピツチ障害抑制方法
US5053080A (en) * 1990-11-20 1991-10-01 W. R. Grace & Co.-Conn. Stabilized asphalt
EP0641884A1 (fr) * 1993-09-07 1995-03-08 Air Products And Chemicals, Inc. Recupération chimique amélioré à partir de liqueur noire
WO1996026316A1 (fr) * 1995-02-23 1996-08-29 Thor Technology Corporation Regulation de la viscosite de la liqueur noire
US5635027A (en) * 1995-04-03 1997-06-03 North Carolina State University Method of reducing the viscosity of a black liquor

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4032473A (en) * 1975-06-04 1977-06-28 Associated Chemists, Inc. Water-based defoamer compositions
EP0194845A2 (fr) * 1985-03-11 1986-09-17 Research Association of Pulp and Paper Technology Procédé pour la concentration d'une liqueur noire
JPS61245391A (ja) * 1985-04-18 1986-10-31 株式会社片山化学工業研究所 紙・パルプ工場におけるピツチ障害抑制方法
US5053080A (en) * 1990-11-20 1991-10-01 W. R. Grace & Co.-Conn. Stabilized asphalt
EP0641884A1 (fr) * 1993-09-07 1995-03-08 Air Products And Chemicals, Inc. Recupération chimique amélioré à partir de liqueur noire
WO1996026316A1 (fr) * 1995-02-23 1996-08-29 Thor Technology Corporation Regulation de la viscosite de la liqueur noire
US5635027A (en) * 1995-04-03 1997-06-03 North Carolina State University Method of reducing the viscosity of a black liquor
US5900112A (en) * 1995-04-03 1999-05-04 North Carolina State University Method of reducing the viscosity of a black liquor using thiocyanate salt

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 198650, Derwent World Patents Index; Class A97, AN 1986-328971, XP002129686 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6737443B1 (en) * 1998-02-23 2004-05-18 Polyphalt Inc. Lignin based colloidal compositions

Also Published As

Publication number Publication date
AU1023900A (en) 2000-05-29

Similar Documents

Publication Publication Date Title
EP1190137B1 (fr) Procede pour separer de la biomasse contenant de la lignocellulose
JP7504856B2 (ja) 架橋クラフトパルプの組成物及び方法
US4088505A (en) Anionic bituminous emulsions
US4455149A (en) Process for the production of fuel compositions
JPH05502480A (ja) 化学―機械的及び／又は化学―熱―機械的木材パルプの製造
AU2023201426B2 (en) Crosslinked pulps, cellulose ether products made therefrom; and related methods of making pulps and cellulose ether products
CH630642A5 (de) Verfahren zur herstellung von ozoniertem ligninsulfonat.
DE102016225827B4 (de) Zweistufiges Aufschlussverfahren zur chemischen Fraktionierung von Lignocellulose
PL155015B1 (en) Method of reducing viscosity and increasing evaportative power of black sulfate lye
CN110832139A (zh) 纳米木质纤维素组合物以及用于生产这些组合物的方法
US5250152A (en) Ethoxylated alcohol and dialkylphenol surfactants as Kraft pulping additives for reject reduction and yield increase
WO2000028135A1 (fr) Traitement de lessive noire
Ruwoldt et al. Carboxylation of lignin by oxidation with hydrogen peroxide and its use as emulsion stabilizer
US5053080A (en) Stabilized asphalt
US3874991A (en) Polysulfide impregnation of lignocellulosic materials in a continuous digester
US6737443B1 (en) Lignin based colloidal compositions
DE69703351T2 (de) Verfahren zum deinken von altpapier
EP1058713A1 (fr) Compositions colloidales a base de lignine
Roberts et al. Controlled black liquor viscosity reduction through salting‐in
Bessa et al. Synthesis of carboxymethylcellulose from corn straw waste: comparison between pre-treatments with sodium hydroxide and low-cost ionic liquid
CN1922359A (zh) 降低高得率纸浆的抽提物含量的方法以及生产漂白的高得率纸浆的方法
EP2029808A2 (fr) Procédé de préparation de matière fibreuse à partir de bois
CZ10893A3 (en) Method of removing lignin from raw cellulose
US4427449A (en) Anionic bituminous emulsions
Borenius LIGNIN AND HEMICELLULOSE IN DIS-PERSIONS–AS SURFACTANTS AND FUNCTIONAL MATERIALS

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref country code: AU

Ref document number: 2000 10239

Kind code of ref document: A

Format of ref document f/p: F

AK Designated states

Kind code of ref document: A1

Designated state(s): AE AL AM AT AU AZ BA BB BG BR BY CA CH CN CR CU CZ DE DK DM EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

NENP Non-entry into the national phase

Ref country code: CA

122 Ep: pct application non-entry in european phase