EP0502052B1 - Verfahren zur herstellung von aufschlusslösungen mit hoher sulfidität für das kochen von sulfatpulpe - Google Patents

Verfahren zur herstellung von aufschlusslösungen mit hoher sulfidität für das kochen von sulfatpulpe Download PDF

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Publication number
EP0502052B1
EP0502052B1 EP90917424A EP90917424A EP0502052B1 EP 0502052 B1 EP0502052 B1 EP 0502052B1 EP 90917424 A EP90917424 A EP 90917424A EP 90917424 A EP90917424 A EP 90917424A EP 0502052 B1 EP0502052 B1 EP 0502052B1
Authority
EP
European Patent Office
Prior art keywords
sodium
sulphur
cooking
reactor
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.)
Expired - Lifetime
Application number
EP90917424A
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English (en)
French (fr)
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EP0502052A1 (de
Inventor
Mats-Olov Hedblom
Hans Lindberg
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.)
Chemrec AB
Nouryon Pulp and Performance Chemicals AB
Original Assignee
Eka Nobel AB
Chemrec AB
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Publication of EP0502052A1 publication Critical patent/EP0502052A1/de
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Anticipated expiration legal-status Critical
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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 cooking.
  • Sodium sulphide and the closely related chemical sodium hydrogen sulphide are often interchangeable with each other and the application thereof often differs in order to meet different sulphidity demands.
  • the aqueous phase sodium sulphide hydrolyzes completely or partly to sodium hydroxide and sodium hydrogen sulphide according to Na2S + H2O -> NaOH + NaSH (1)
  • the concept sulphidity in the pulp industry is usually expressed as wherein NaSH and NaOH are expressed in molar units. This means e.g. that an aqueous solution containing sodium hydrogen sulphide and sodium hydroxide having a sulphidity of 40% contains 4 times more moles of sodium hydroxide than sodium hydrogen sulphide.
  • the equilibrium (1) expresses a solution having a sulphidity of 100%.
  • a typical green liquor has the composition Sodium carbonate 90-105 g/l Sodium sulphide 20-50 g/l Sodium hydroxide 15-25 g/l (all substances calculated as sodium hydroxide).
  • the green liquor obtained is converted to white liquor according to the known causticizing process, see for example US-A-4098639
  • the composition of a white liquor may vary from mill to mill but approximate concentration values are Sodium hydroxide, NaOH 80-120 g/l Sodium sulphide, Na2S 20-50 g/l Sodium carbonate, Na2CO3 10-30 g/l Sodium sulphate, Na2SO4 5-10 g/l (all substances calculated as sodium hydroxide).
  • Na2S is estimated to be fully hydrolyzed according to Na2S + H2O -> 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.
  • Modified cooking according to the present technique is based upon the following process conditions:
  • 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 cooking liquor is added at two or several places.
  • An extra high sulphidity in the cooking liquor added in the beginning of the cooking is of greatest use while the sulphidity in cooking liquors added in the final phase of the cooking may be low.
  • 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.
  • the sodium sulphide melt obtained in the process of the invention may be dissolved in water and further processed to cooking liquor in a way known per se .
  • a solution of the melt is fed directly to the digester for optimum use of its high sulphidity in modified cooking.
  • a solution of the melt is mixed with part of the white liquor prepared in the usual way.
  • 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 large in order for the reaction to have time to take place, i.e. 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 700°C.
  • 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.
  • 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 sulphate, sodium sulphite, sodium hydrogen sulphite and sodium thiosulphate.
  • elemental sulphur may be used or any other sulphur-containing chemical having a Na/S ratio being equal to or below about 4.
  • 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 750°C 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-A-0258196. 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 Na2CO3.

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

Claims (6)

  1. Verfahren zur Herstellung, unter reduzierenden Bedingungen, von Kochlaugen mit hoher Sulfidität fur den Sulfatzellstoff-Aufschluß, wobei die bei dem Aufschlußverfahren gebildete Schwarzlauge nach dem Eindampfen vollständig oder teilweise einem bei erhöhter Temperatur betriebenen Reaktor zugeführt wird, welche durch Energiezufuhr von einer äußeren Wärmequelle und/oder Energiefreisetzung aus der Schwarzlauge erzielt wird, wobei eine im wesentlichen aus Natriumsulfid bestehende Schmelze gebildet und zur weiteren Verarbeitung zu Kochlauge abgezogen wird, dadurch gekennzeichnet, daß zusätzlich dem Reaktor die gesamten oder ein Teil der in der Zellstoffmühle vorhandenen schwefelhaltigen und/oder schwefel- und natriumhaltigen Materialien, einschließlich den schwefelhaltigen und/oder natrium- und schwefelhaltigen Ergänzungschemikalien, welche für die Gesamtchemikalienbilanz der Zellstoffmühle eingesetzt werden, in der Weise zugeführt werden, daß das Molverhältnis von Natrium zu Schwefel in der dem Reaktor zugeführten Gesamtmischung innerhalb des Bereichs von 1,5 bis 4 liegt.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Molverhältnis von Natrium zu Schwefel in der dem Reaktor zugeführten Gesamtmischung innerhalb des Bereichs von 2 bis 3, vorzugsweise von 2 bis 2,8, liegt.
  3. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die in der Zellstoffmühle vorliegenden und teilweise oder vollständig dem Reaktor zugeführten schwefelhaltigen und/oder schwefel- und natriumhaltigen Materialien aus einem, mehreren oder sämtlichen der folgenden Materialien bestehen: Elektrofilterasche, Restprodukt aus der Chlordioxidherstellung, Natriumhydrogensulfit enthaltende Lösungen aus der Wäsche von Schwefeldioxid, Ablaugen vom CTMP, NSSC oder anderen Sulfitzellstoffverfahren. Schwefeldioxid aus dem Rösten bzw. Glühen von Kupfersulfid sowie Schwefelwasserstoff enthaltende Kondensate oder Luftströme.
  4. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die schwefelhaltigen und/oder schwefel- und natriumhaltigen Ergänzungschemikalien aus einem oder mehreren aus Schwefel, Schwefeldioxid, Schwefelsäure, Natriumsulfit, Natriumhydrogensulfat, Natriumthiosulfat oder Natriumsulfat bestehen.
  5. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Natriumsulfidschmelze oder eine wäßrige Lösung davon mit der Weißlauge vermischt wird, wobei eine Weißlauge mit erhöhter Sulfidität erhalten wird.
  6. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß eine wäßrige Lösung der Natriumsulfidschmelze beim sogenannten modifizierten Sulfataufschluß verwendet wird.
EP90917424A 1989-11-23 1990-11-21 Verfahren zur herstellung von aufschlusslösungen mit hoher sulfidität für das kochen von sulfatpulpe Expired - Lifetime EP0502052B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
SE8903953 1989-11-23
SE8903953A SE465039B (sv) 1989-11-23 1989-11-23 Saett att framstaella koklutar med hoeg sulfiditet foer sulfatmassakokning
PCT/SE1990/000751 WO1991008337A1 (en) 1989-11-23 1990-11-21 A process for the preparation of cooking liquors having high sulphidity for sulphate pulp cooking

Publications (2)

Publication Number Publication Date
EP0502052A1 EP0502052A1 (de) 1992-09-09
EP0502052B1 true EP0502052B1 (de) 1994-10-05

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP90917424A Expired - Lifetime EP0502052B1 (de) 1989-11-23 1990-11-21 Verfahren zur herstellung von aufschlusslösungen mit hoher sulfidität für das kochen von sulfatpulpe

Country Status (18)

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

Families Citing this family (14)

* 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
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
FI92725C (fi) * 1991-09-09 1994-12-27 Ahlstroem Oy Menetelmä keittolipeän valmistamiseksi
FI914586A (fi) * 1991-09-27 1993-03-28 Ahlstroem Oy Foerfarande foer foerminskning av asklasten av en cellufabriks pannanlaeggning
SE468600B (sv) * 1991-12-16 1993-02-15 Chemrec Ab Saett att framstaella koklut med hoeg sulfiditet
SE9300199L (sv) * 1993-01-25 1994-07-26 Kvaerner Pulping Tech Metod vid återvinning av cellulosaavlutar
US6030493A (en) 1994-11-04 2000-02-29 Kvaerner Pulping, Ab Process for recovering chemicals and energy from cellulose spent liquor using multiple gasifiers
SE518735C2 (sv) * 1999-10-13 2002-11-12 Chemrec Ab Förfarande och anordning vid utvinning av kemikalier i samband med förgasning av restprodukter från massaframställning
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
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
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
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

Family Cites Families (6)

* 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
SE447400B (sv) * 1985-03-26 1986-11-10 Skf Steel Eng Ab Sett och anordning for kemikalieatervinning av massaavlutar i konventionell sodapanna
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

Also Published As

Publication number Publication date
SE465039B (sv) 1991-07-15
FI922288A (fi) 1992-05-20
AU6883691A (en) 1991-06-26
ZA909337B (en) 1991-09-25
NO921962D0 (no) 1992-05-19
MX173408B (es) 1994-03-01
JPH05502274A (ja) 1993-04-22
EP0502052A1 (de) 1992-09-09
CN1030003C (zh) 1995-10-11
FI922288A0 (fi) 1992-05-20
WO1991008337A1 (en) 1991-06-13
RU2067637C1 (ru) 1996-10-10
AU662882B2 (en) 1995-09-21
CA2069107A1 (en) 1991-05-24
CN1051953A (zh) 1991-06-05
DE69013159D1 (de) 1994-11-10
DE69013159T2 (de) 1995-03-09
NO176109C (no) 1995-02-01
SE8903953L (sv) 1991-05-24
AR243947A1 (es) 1993-09-30
BR9007837A (pt) 1992-08-25
FI103902B1 (fi) 1999-10-15
FI103902B (fi) 1999-10-15
ATE112595T1 (de) 1994-10-15
JP2815701B2 (ja) 1998-10-27
NO176109B (no) 1994-10-24
SE8903953D0 (sv) 1989-11-23
NO921962L (no) 1992-05-20
ES2062569T3 (es) 1994-12-16
MY104532A (en) 1994-04-30
CA2069107C (en) 2002-04-09

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