EP0502052A1 - 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.Info
- Publication number
- EP0502052A1 EP0502052A1 EP90917424A EP90917424A EP0502052A1 EP 0502052 A1 EP0502052 A1 EP 0502052A1 EP 90917424 A EP90917424 A EP 90917424A EP 90917424 A EP90917424 A EP 90917424A EP 0502052 A1 EP0502052 A1 EP 0502052A1
- 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.)
- Granted
Links
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 .
Landscapes
- Paper (AREA)
- Commercial Cooking Devices (AREA)
Abstract
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SE8903953A SE465039B (sv) | 1989-11-23 | 1989-11-23 | Saett att framstaella koklutar med hoeg sulfiditet foer sulfatmassakokning |
SE8903953 | 1989-11-23 | ||
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 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0502052A1 true EP0502052A1 (fr) | 1992-09-09 |
EP0502052B1 EP0502052B1 (fr) | 1994-10-05 |
Family
ID=20377574
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP90917424A Expired - Lifetime 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 |
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 (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
Families Citing this family (13)
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 |
US6027609A (en) | 1994-11-04 | 2000-02-22 | Kvaener Pulping Ab | Pulp-mill recovery installation 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)
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 |
IL80678A (en) * | 1985-11-19 | 1999-05-09 | Schering Biotech Corp | Human interleukin-4 |
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 |
-
1989
- 1989-11-23 SE SE8903953A patent/SE465039B/sv not_active IP Right Cessation
-
1990
- 1990-11-21 AR AR90318435A patent/AR243947A1/es active
- 1990-11-21 MX MX023395A patent/MX173408B/es unknown
- 1990-11-21 WO PCT/SE1990/000751 patent/WO1991008337A1/fr active IP Right Grant
- 1990-11-21 CN CN90109309A patent/CN1030003C/zh not_active Expired - Fee Related
- 1990-11-21 AT AT90917424T patent/ATE112595T1/de not_active IP Right Cessation
- 1990-11-21 RU SU905052326A patent/RU2067637C1/ru active
- 1990-11-21 ES ES90917424T patent/ES2062569T3/es not_active Expired - Lifetime
- 1990-11-21 MY MYPI90002045A patent/MY104532A/en unknown
- 1990-11-21 CA CA002069107A patent/CA2069107C/fr not_active Expired - Lifetime
- 1990-11-21 ZA ZA909337A patent/ZA909337B/xx unknown
- 1990-11-21 EP EP90917424A patent/EP0502052B1/fr not_active Expired - Lifetime
- 1990-11-21 AU AU68836/91A patent/AU662882B2/en not_active Ceased
- 1990-11-21 JP JP3500321A patent/JP2815701B2/ja not_active Expired - Fee Related
- 1990-11-21 BR BR909007837A patent/BR9007837A/pt not_active IP Right Cessation
- 1990-11-21 DE DE69013159T patent/DE69013159T2/de not_active Expired - Fee Related
-
1992
- 1992-05-19 NO NO921962A patent/NO176109C/no unknown
- 1992-05-20 FI FI922288A patent/FI103902B/fi active
Non-Patent Citations (1)
Title |
---|
See references of WO9108337A1 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
Also Published As
Publication number | Publication date |
---|---|
DE69013159D1 (de) | 1994-11-10 |
CN1030003C (zh) | 1995-10-11 |
SE8903953L (sv) | 1991-05-24 |
CA2069107A1 (fr) | 1991-05-24 |
WO1991008337A1 (fr) | 1991-06-13 |
MX173408B (es) | 1994-03-01 |
RU2067637C1 (ru) | 1996-10-10 |
JPH05502274A (ja) | 1993-04-22 |
BR9007837A (pt) | 1992-08-25 |
AR243947A1 (es) | 1993-09-30 |
NO176109C (no) | 1995-02-01 |
EP0502052B1 (fr) | 1994-10-05 |
FI103902B1 (fi) | 1999-10-15 |
JP2815701B2 (ja) | 1998-10-27 |
AU6883691A (en) | 1991-06-26 |
AU662882B2 (en) | 1995-09-21 |
ES2062569T3 (es) | 1994-12-16 |
FI103902B (fi) | 1999-10-15 |
MY104532A (en) | 1994-04-30 |
CN1051953A (zh) | 1991-06-05 |
ZA909337B (en) | 1991-09-25 |
NO921962D0 (no) | 1992-05-19 |
SE465039B (sv) | 1991-07-15 |
FI922288A0 (fi) | 1992-05-20 |
NO176109B (no) | 1994-10-24 |
ATE112595T1 (de) | 1994-10-15 |
CA2069107C (fr) | 2002-04-09 |
SE8903953D0 (sv) | 1989-11-23 |
NO921962L (no) | 1992-05-20 |
FI922288A (fi) | 1992-05-20 |
DE69013159T2 (de) | 1995-03-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
AU662882B2 (en) | A process for the preparation of cooking liquors having high sulphidity for sulphate pulp cooking | |
JP2796477B2 (ja) | パルプ工場における白液選択酸化法と酸化白液の製法ならびに酸化反応系操作の制御法 | |
EP0599917B1 (fr) | Production d'hydroxyde de metal alcalin et regeneration des liqueurs noirs | |
EP0617747B2 (fr) | Methode d'elaboration de liqueur de digestion | |
US6663749B2 (en) | Method for regenerating sodium hydroxide by partial autocausticizing sodium carbonate containing smelt by reaction with borate | |
US5405496A (en) | Process for the preparation of cooking liquors having high sulphidity for sulphate pulp cooking | |
US5328563A (en) | Method of treating material containing sodium sulphate and/or sodium carbonate in a pulp mill | |
US5080756A (en) | Kraft pulping process with spent sulphuric acid addition to strong black liquor | |
US5326433A (en) | Multi-level sulfide content white liquor production and utilization in cellulose pulping | |
CA2160008C (fr) | Methode de conversion de sulfate de sodium | |
US20050076568A1 (en) | Partial oxidation of cellulose spent pulping liquor | |
US5597445A (en) | Method for recovering sodium from a spent cooking liquor | |
WO2001027384A1 (fr) | Procede et dispositif de recuperation de produits chimiques presents dans des cendres volantes lors d'un processus de gazeification | |
US1860570A (en) | Manufacture of pulp, etc. | |
FI116074B (fi) | Rikin kierrätys sulfaattiselluprosessissa | |
JP2000345487A (ja) | リグノセルロースパルプの製造方法 | |
US1795756A (en) | Production of chemical pulp | |
CA2163852A1 (fr) | Utilisation de liqueur blanche oxydee | |
WO1997036043A1 (fr) | Procede d'extraction de produits chimiques et d'energie de liqueur cellulosique usee |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 19920522 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT DE ES FR SE |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: CHEMREC AKTIEBOLAG Owner name: EKA NOBEL AB |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: EKA NOBEL AB Owner name: CHEMREC AKTIEBOLAG |
|
17Q | First examination report despatched |
Effective date: 19930608 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT DE ES FR SE |
|
REF | Corresponds to: |
Ref document number: 112595 Country of ref document: AT Date of ref document: 19941015 Kind code of ref document: T |
|
REF | Corresponds to: |
Ref document number: 69013159 Country of ref document: DE Date of ref document: 19941110 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2062569 Country of ref document: ES Kind code of ref document: T3 |
|
ET | Fr: translation filed | ||
EAL | Se: european patent in force in sweden |
Ref document number: 90917424.5 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19961025 Year of fee payment: 7 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 19961026 Year of fee payment: 7 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 19961121 Year of fee payment: 7 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 19961122 Year of fee payment: 7 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19971121 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF THE APPLICANT RENOUNCES Effective date: 19971122 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY Effective date: 19971130 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19980801 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20010402 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 20091126 Year of fee payment: 20 |
|
EUG | Se: european patent has lapsed |