WO1991008337A1 - Procede de preparation de liqueurs de cuisson de sulfidite elevee pour la cuisson de pate a papier au sulfate - Google Patents

Procede de preparation de liqueurs de cuisson de sulfidite elevee pour la cuisson de pate a papier au sulfate Download PDF

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Publication number
WO1991008337A1
WO1991008337A1 PCT/SE1990/000751 SE9000751W WO9108337A1 WO 1991008337 A1 WO1991008337 A1 WO 1991008337A1 SE 9000751 W SE9000751 W SE 9000751W WO 9108337 A1 WO9108337 A1 WO 9108337A1
Authority
WO
WIPO (PCT)
Prior art keywords
sodium
sulphur
cooking
reactor
liquor
Prior art date
Application number
PCT/SE1990/000751
Other languages
English (en)
Inventor
Mats-Olov Hedblom
Hans Lindberg
Original Assignee
Eka Nobel Ab
Chemrec Ab
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 Eka Nobel Ab, Chemrec Ab filed Critical Eka Nobel Ab
Priority to EP90917424A priority Critical patent/EP0502052B1/fr
Priority to BR909007837A priority patent/BR9007837A/pt
Priority to AU68836/91A priority patent/AU662882B2/en
Priority to CA002069107A priority patent/CA2069107C/fr
Priority to DE69013159T priority patent/DE69013159T2/de
Priority to SU905052326A priority patent/RU2067637C1/ru
Publication of WO1991008337A1 publication Critical patent/WO1991008337A1/fr
Priority to NO921962A priority patent/NO176109C/no
Priority to FI922288A priority patent/FI103902B/fi

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • 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
    • D21C11/04—Regeneration of pulp liquors or effluent waste waters of alkali lye

Definitions

  • the present invention relates to a process for the preparation of cooking liquors having high sulphidity for the sulphate pulp industry starting from chemicals available in the pulp mill or make-up chemicals common in the pulp mill.
  • the invention considers the important pulp mill balance between sodium and sulphur and is particularly advantageous in cooking with high sulphidity, particularly in so-called modified
  • NaSH and NaOH are expressed in molar units. This means e.g. that an aqueous solution containing sodium hydrogen
  • the sulphate pulp mills often operate whithin the sulphidity range of 25 to 40% (white liquor sulphidity).
  • a major part of the sodium reacts with carbon dioxide when burning black liquor to form sodium carbonate.
  • the mixture of sodium sulphide and sodium carbonate forms a melt at the bottom of the soda recovery unit and this melt is withdrawn and is reacted with water to form so-called green liquor.
  • a typical green liquor has the composition
  • Chemicals recovery according to the "sulphate process” results in that a relatively large amount of sulphur reaches the oxidative zone and is rejected from the soda recovery unit mainly as sodium sulphate (electrical filter ash) and sulphur dioxide. If the white liquor sulphidity exceeds 35% problems begin to arise i.a. by high emissions of sulphur dioxide from the soda recovery unit. Scrubbing with alkaline medium is therefore often used in order to eliminate or strongly reduce the sulphur dioxide emissions.
  • the green liquor obtained is converted to white liquor according to the known causticizing process.
  • the composition of a white liquor may vary from mill to mill but approximate concentration values are
  • Na 2 S + H 2 O ⁇ NaOH + NaSH this means that the amount of sodium, bound as carbonate, often amounts to more than 20% of the sodium present as hydroxide.
  • the kappa number is a measure of the lignin content and the viscosity is considered to be a measure of the strength of the cellulose fiber. It is of interest to be able to cook the pulp to as low kappa number as possible. This especially applies if it shall be bleached to high (90 ISO) brightness. For this purpose there is required bleaching with chlorine-containing bleaching
  • the alkali concentration shall be as constant as possible during the course of the cooking.
  • the hydrogen sulphide concentration shall be as high as possible, particularly in the beginning of the bulk delignification phase.
  • the hydrogen sulphide concentration can be low at the end phase of the cooking.
  • the concentrations of lignin released and sodium ions shall be as low as possible, particularly in the last stage of the cooking.
  • the temperature shall be low. particularly in the beginning and at the end of the cooking.
  • item 2 is of special interest with regard to the present invention. So far one has been allowed to content with the concentration of hydrogen sulphide ions provided by the 40% sulphidity in the white liquor.
  • the invention relates to a process for preparing, under reducing conditions, cooking liquors having high sulphidity for sulphate pulp cooking wherein the black liquor formed in the cooking process is passed, after evaporation, completely or partly to a reactor operating at an increased temperature which is obtained by energy supply from an external heat source and/or release of energy from the black liquor, a melt essentially consisting of sodium sulphide being formed and withdrawn to be further processed to cooking liquor.
  • the process of the invention is characterized in that in addition there are added to the reactor the whole or part of the sulphur- containing and/or sulphur- and sodium-containing materials present in the pulp mill, including sulphur-containing and/or sodium- and sulphur-containing make-up chemicals used for the total chemicals balance of the pulp mill, in such a way that the mole ratio of sodium to sulphur in the total mixture fed to the reactor is within the range from 1.5 to 4.
  • a solution of the melt is fed directly to the
  • additional energy in addition to the energy released from the black liquor in partial oxidation, can be supplied to the mixing zone of the reactor by a hot gas, the heat content and oxidation potential of which are adjusted to the reduction work required.
  • the heat energy may e.g. be supplied by a gas heated by a plasma generator.
  • the very hot gas or gas mixture can also be formed directly or indirectly with an oxy-fuel burner.
  • gas or gas mixture use can be made of air, recirculating process gas, hydrogen gas, natural gas, carbon monoxide, etc.
  • gas or gas mixture is obtained by combustion of e.g. acetylene or liquified petroleum gas with oxygen enriched air or pure oxygen gas.
  • a preferred process according to the invention is that the hot gas is fed to the reactor close to the material fed which in turn must be finely divided which can be obtained by different kinds of atomization techniques known by the man skilled in the art.
  • the design of the reactor must be sufficiently
  • the reactor volume must ensure a certain minimum residence time.
  • the reactor is preferrably a closed reaction vessel and the temperature in the reactor shall be at least the temperature at which the sodium sulphide is formed under otherwise prevailing conditions.
  • the man skilled in the art may establish said temperature from case to case, e.g. by routine experiments.
  • the temperature is preferrably not below 700oC.
  • the pressure in the reactor is preferrably atmospheric pressure. However, the process may be effected at an increased pressure, e.g. in order to reduce the reactor volume.
  • Swedish Patent SE 8501465-2 there is disclosed a process to relieve the soda recovery unit by means of plasma gasification of a partial stream of the black liquor. This makes its
  • the mole ratio of sodium to sulphur in the total mixture fed to the reactor is below about 4 and is within the range from 1.5 to 4, preferrably from 2 to 3.
  • This adjustment of the sodium to sulphur ratio is effected by means of sulphur- containing and/or sulphur- and sodium-containing materials present in the pulp mill, including sulphur-containing and/or sodium- and sulphur-containing make-up chemicals used for the total chemicals balance of the pulp mill.
  • the make-up chemicals used in order to adjust the mole ratio of sodium to sulphur correctly may consist of sulphur, sulphur dioxide, sulphuric acid, sodium hydrogen sulphate, sodium
  • elemental sulphur may be used or any other sulphur- containing chemical having a Na/S ratio being equal to or below about 4.
  • Example 1 The invention is further illustrated by means of the following working examples.
  • Example 1 The invention is further illustrated by means of the following working examples.
  • the following material streams were fed continuously per hour to a reactor operating at atmospheric pressure. - 620 kg black liquor (65% dry substance content) containing 129 kg sodium (Na) and 35 kg sulphur (S) per ton of black liquor. - a residual acid mixture from chlorine dioxide production according to the Mathieson process containing 80 kg H 2 SO 4 and 62 kg Na 2 SO 4 - 800 kg Na 2 SO 4 in the form of electrical filter ash.
  • the above material streams were mixed with an oxygen-containing gas and passed to a reaction room.
  • the oxygen-containing gas was heated to about 750oC in a plasma generator.
  • a major part of the energy content of the liquor may be released by partial oxidation whereby it is not necessary to preheat the oxygen-containing gas in a plasma generator.
  • Example 2 One proceeded in exactly the same way as in Example 1 and obtained a melt phase which that was withdrawn from the system.
  • the sulphur dioxide added had been generated by roasting according to the process for preparation of sulphide-free liquor disclosed in EP 87850238.4. From the melt prepared there was prepared a 4.0 molar solution with regard to sodium containing 1.75 moles of NaOH, 1.75 moles of NaSH and 0.25 moles of Na 2 CO 3 .

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  • Paper (AREA)
  • Commercial Cooking Devices (AREA)

Abstract

Procédé de préparation, dans des conditions de réduction, de liqueurs de cuisson de sulfidité élevée pour la cuisson de pâte au sulfate, dans lequel la liqueur noire obtenue dans le procédé de cuisson est acheminée, après évaporation, complètement ou partiellement à un réacteur fonctionnant à une température élevée, laquelle est obtenue par une alimentation en énergie provenant d'une source de chaleur extérieure et/ou la libération d'énergie provenant de la liqueur noire, une fusion composée essentiellement de sulfure de sodium étant formée et retirée pour être traitée à nouveau afin d'obtenir une liqueur de cuisson. Le procédé de l'invention est caractérisé en ce que le réacteur reçoit également tout ou partie des matières contenant du soufre et/ou contenant du soufre et du sodium, présentes dans la fabrique de pâte à papier, parmi lesquelles les agents chimiques d'appoint contenant du soufre et/ou contenant du sodium et du soufre, utilisés dans le solde des agents chimiques totaux de la fabrique de pâte à papier, de sorte que le rapport molaire entre le sodium et le soufre dans le mélange total acheminé au réacteur, se situe dans la plage comprise entre 1,5 et 4. Selon le mode de réalisation préféré de l'invention, on utilise une solution aqueuse de la fusion de sulfure de sodium obtenue dans ladite cuisson au sulfate modifié.
PCT/SE1990/000751 1989-11-23 1990-11-21 Procede de preparation de liqueurs de cuisson de sulfidite elevee pour la cuisson de pate a papier au sulfate WO1991008337A1 (fr)

Priority Applications (8)

Application Number Priority Date Filing Date Title
EP90917424A EP0502052B1 (fr) 1989-11-23 1990-11-21 Procede de preparation de liqueurs de cuisson de sulfidite elevee pour la cuisson de pate a papier au sulfate
BR909007837A BR9007837A (pt) 1989-11-23 1990-11-21 Processo para preparacao,sob condicoes de reducao de licores de cozimento
AU68836/91A AU662882B2 (en) 1989-11-23 1990-11-21 A process for the preparation of cooking liquors having high sulphidity for sulphate pulp cooking
CA002069107A CA2069107C (fr) 1989-11-23 1990-11-21 Procede de preparation de lessives de cuisson a haute teneur en sulfures pour la fabrication de pate au sulfate
DE69013159T DE69013159T2 (de) 1989-11-23 1990-11-21 Verfahren zur herstellung von aufschlusslösungen mit hoher sulfidität für das kochen von sulfatpulpe.
SU905052326A RU2067637C1 (ru) 1989-11-23 1990-11-21 Способ приготовления варочного раствора для сульфатного способа варки целлюлозы
NO921962A NO176109C (no) 1989-11-23 1992-05-19 Fremgangsmåte til fremstilling av kokevæsker med höy sulfiditet for sulfatmassekoking
FI922288A FI103902B (fi) 1989-11-23 1992-05-20 Menetelmä keittolipeiden, joilla on korkea sulfidisuus, valmistamiseksi sukfaattisellun keittämiseksi

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE8903953-1 1989-11-23
SE8903953A SE465039B (sv) 1989-11-23 1989-11-23 Saett att framstaella koklutar med hoeg sulfiditet foer sulfatmassakokning

Publications (1)

Publication Number Publication Date
WO1991008337A1 true WO1991008337A1 (fr) 1991-06-13

Family

ID=20377574

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/SE1990/000751 WO1991008337A1 (fr) 1989-11-23 1990-11-21 Procede de preparation de liqueurs de cuisson de sulfidite elevee pour la cuisson de pate a papier au sulfate

Country Status (18)

Country Link
EP (1) EP0502052B1 (fr)
JP (1) JP2815701B2 (fr)
CN (1) CN1030003C (fr)
AR (1) AR243947A1 (fr)
AT (1) ATE112595T1 (fr)
AU (1) AU662882B2 (fr)
BR (1) BR9007837A (fr)
CA (1) CA2069107C (fr)
DE (1) DE69013159T2 (fr)
ES (1) ES2062569T3 (fr)
FI (1) FI103902B (fr)
MX (1) MX173408B (fr)
MY (1) MY104532A (fr)
NO (1) NO176109C (fr)
RU (1) RU2067637C1 (fr)
SE (1) SE465039B (fr)
WO (1) WO1991008337A1 (fr)
ZA (1) ZA909337B (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2681883A1 (fr) * 1991-09-27 1993-04-02 Ahlstroem Oy Procede de traitement d'une cendre provenant de la fabrication de pate de cellulose.
WO1993012288A1 (fr) * 1991-12-16 1993-06-24 Chemrec Aktiebolag Methode d'elaboration de liqueur de digestion
US5326433A (en) * 1991-02-06 1994-07-05 Ahlstrom Recovery Inc. Multi-level sulfide content white liquor production and utilization in cellulose pulping
WO1994017240A1 (fr) * 1993-01-25 1994-08-04 Kvaerner Pulping Technologies Ab Procede de recuperation de liqueurs de cellulose epuisees
US5340440A (en) * 1991-09-09 1994-08-23 A. Ahlstrom Corporation Method for recovering chemicals using recovery boiler having at least 2 different melt sections
WO2001027384A1 (fr) * 1999-10-13 2001-04-19 Kvaerner Chemrec Ab Procede et dispositif de recuperation de produits chimiques presents dans des cendres volantes lors d'un processus de gazeification

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5213663A (en) * 1991-07-22 1993-05-25 The Foxboro Company Method for controlling the sodium carbonate concentration of green liquor in the dissolving tank
US6030493A (en) 1994-11-04 2000-02-29 Kvaerner Pulping, Ab Process for recovering chemicals and energy from cellulose spent liquor using multiple gasifiers
CN1087045C (zh) * 2000-03-17 2002-07-03 中国科学院生态环境研究中心 碱法制浆造纸黑液良性循环资源化处理新工艺
CL2010001609A1 (es) * 2010-12-29 2011-03-18 Univ De Concepcion 50% Proceso para obtener tall oil util que comprende la reaccion entre una solucion de sesquisulfato de sodio y jabon de tall oil.
CN103510418B (zh) * 2012-06-25 2016-03-30 北京英力生科新材料技术有限公司 一种无黑液化学制浆工艺
CN103726376A (zh) * 2013-12-30 2014-04-16 中冶美利纸业股份有限公司 阔叶木材间歇式低温快速制浆工艺
CN103726375A (zh) * 2013-12-30 2014-04-16 中冶美利纸业股份有限公司 一种沙柳亚硫酸盐法制浆工艺
FI130066B (en) * 2019-02-13 2023-01-31 Andritz Oy Process for replacing sodium losses in a pulp mill and process for producing bleached cellulosic pulp

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4098639A (en) * 1975-06-17 1978-07-04 Mo Och Domsjo Aktiebolag Process for reducing the requirement of fresh chemicals without increasing emissions in the pulping of cellulosic material
US4710269A (en) * 1985-03-26 1987-12-01 Skf Steel Engineering Ab Recovering chemicals from spent pulp liquors

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PT83761B (pt) * 1985-11-19 1989-06-30 Schering Biotech Corp Metodo para a producao de interleuquina-4 de mamifero
JPS62166881A (ja) * 1986-01-16 1987-07-23 Michio Matsuhashi 大腸菌のペリプラズム蛋白質分泌変異株
AU589540B2 (en) * 1986-08-14 1989-10-12 Alby Klorat Ab A process for the preparation of sulphide-free alkali liquor
JPS63237790A (ja) * 1987-03-27 1988-10-04 Toyo Jozo Co Ltd ＯｍｐＡシグナルペプチドを用いたヒトス−パ−オキシドデイスムタ−ゼ及びグラム陰性細菌による細胞外分泌生産

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4098639A (en) * 1975-06-17 1978-07-04 Mo Och Domsjo Aktiebolag Process for reducing the requirement of fresh chemicals without increasing emissions in the pulping of cellulosic material
US4710269A (en) * 1985-03-26 1987-12-01 Skf Steel Engineering Ab Recovering chemicals from spent pulp liquors

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5326433A (en) * 1991-02-06 1994-07-05 Ahlstrom Recovery Inc. Multi-level sulfide content white liquor production and utilization in cellulose pulping
US5340440A (en) * 1991-09-09 1994-08-23 A. Ahlstrom Corporation Method for recovering chemicals using recovery boiler having at least 2 different melt sections
FR2681883A1 (fr) * 1991-09-27 1993-04-02 Ahlstroem Oy Procede de traitement d'une cendre provenant de la fabrication de pate de cellulose.
WO1993012288A1 (fr) * 1991-12-16 1993-06-24 Chemrec Aktiebolag Methode d'elaboration de liqueur de digestion
US5660685A (en) * 1991-12-16 1997-08-26 Chemrec Aktiebolag Gasifying black liquor with recycling of generated hydrogen sulphide gas to the gasifier
WO1994017240A1 (fr) * 1993-01-25 1994-08-04 Kvaerner Pulping Technologies Ab Procede de recuperation de liqueurs de cellulose epuisees
US5746886A (en) * 1993-01-25 1998-05-05 Kvaerner Pulping Ab Method for the recovery of energy and chemicals from cellulose spent liquor containing potassium using a gasifier
WO2001027384A1 (fr) * 1999-10-13 2001-04-19 Kvaerner Chemrec Ab Procede et dispositif de recuperation de produits chimiques presents dans des cendres volantes lors d'un processus de gazeification

Also Published As

Publication number Publication date
DE69013159D1 (de) 1994-11-10
MY104532A (en) 1994-04-30
ATE112595T1 (de) 1994-10-15
NO921962D0 (no) 1992-05-19
CA2069107A1 (fr) 1991-05-24
ES2062569T3 (es) 1994-12-16
NO921962L (no) 1992-05-20
ZA909337B (en) 1991-09-25
FI922288A (fi) 1992-05-20
JPH05502274A (ja) 1993-04-22
NO176109C (no) 1995-02-01
SE8903953L (sv) 1991-05-24
AR243947A1 (es) 1993-09-30
FI922288A0 (fi) 1992-05-20
FI103902B1 (fi) 1999-10-15
EP0502052B1 (fr) 1994-10-05
CA2069107C (fr) 2002-04-09
MX173408B (es) 1994-03-01
CN1030003C (zh) 1995-10-11
JP2815701B2 (ja) 1998-10-27
BR9007837A (pt) 1992-08-25
AU6883691A (en) 1991-06-26
NO176109B (no) 1994-10-24
DE69013159T2 (de) 1995-03-09
SE465039B (sv) 1991-07-15
EP0502052A1 (fr) 1992-09-09
AU662882B2 (en) 1995-09-21
SE8903953D0 (sv) 1989-11-23
FI103902B (fi) 1999-10-15
RU2067637C1 (ru) 1996-10-10
CN1051953A (zh) 1991-06-05

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