EP0593744A1 - Procede de recuperation de produits chimiques de cuisson a partir de la liqueur noire dans la fabrication de la cellulose selon le procede organosolver - Google Patents

Procede de recuperation de produits chimiques de cuisson a partir de la liqueur noire dans la fabrication de la cellulose selon le procede organosolver

Info

Publication number
EP0593744A1
EP0593744A1 EP93911419A EP93911419A EP0593744A1 EP 0593744 A1 EP0593744 A1 EP 0593744A1 EP 93911419 A EP93911419 A EP 93911419A EP 93911419 A EP93911419 A EP 93911419A EP 0593744 A1 EP0593744 A1 EP 0593744A1
Authority
EP
European Patent Office
Prior art keywords
oxidation
cooking
process according
aqueous phase
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
Application number
EP93911419A
Other languages
German (de)
English (en)
Other versions
EP0593744B1 (fr
Inventor
Otto W. Gordon
Eric Plattner
Frank Doppenberg
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.)
Granit SA
Original Assignee
Granit SA
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 Granit SA filed Critical Granit SA
Publication of EP0593744A1 publication Critical patent/EP0593744A1/fr
Application granted granted Critical
Publication of EP0593744B1 publication Critical patent/EP0593744B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • D21C3/20—Pulping cellulose-containing materials with organic solvents or in solvent environment
    • 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
    • D21C11/0057—Oxidation of liquors, e.g. in order to reduce the losses of sulfur compounds, followed by evaporation or combustion if the liquor in question is a black liquor

Definitions

  • the invention relates to a process for the recovery of sodium hydroxide solution from the black liquor of the pulp manufacture by partial or complete wet-oxidation of the organic components with air and or or oxygen.
  • the cooking liquors In addition to lignin, hemicelluloses, sugar and resins, the cooking liquors also contain considerable amounts of 25 carboxylic acids as alkali salts.
  • Inert gases and water vapor (7) escape from the reactor and are treated separately.
  • the oxidation in the aqueous phase allows lignin, hemicelluloses, sugars and resins to be burned without significantly oxidizing the sodium salts of organic carboxylic acids such as acetic acid.
  • This selective combustion allows the residence time in the combustion reactor to be greatly reduced, which results in a large downsizing of the plant.
  • the liquid which has been treated by wet oxidation and which comes from the reactor contains, in addition to the alkaline salts of carbonic and organic acids, no or only a small proportion of other substances.
  • the alkali carbonates or bicarbonates contained in this solution can be easily and completely converted by caustification (8) into almost colorless lye, e.g. sodium hydroxide solution, which is returned to the cooking process with the unchanged salts of the organic acids. (9).
  • the salts of the organic acids for example after cooling Sodium acetate, are brought to crystallization (10), the sodium hydroxide solution remaining in solution.
  • the sodium hydroxide solution is mixed with sodium acetate
  • Electrodialysis can be broken down into sodium hydroxide solution and acetic acid.
  • the precipitation with carbon dioxide e.g. flue gas
  • acetic acid which has the advantage that lower pH values and thus more complete lignin precipitation can be achieved.
  • the oxidation in the aqueous phase also releases a substantial amount of thermal energy, which can be used for the concentration of the black liquor, but also for the cooking process.
  • the process is used in particular on black liquors, which originate, for example, from an Organosolv or a soda process for the production of cellulose, after or even before the lignins (1, 2) have been separated off
  • the oxidation provides energy in the form of steam, which can be reused in the aforementioned processes.
  • This solution was introduced into the oxidation reactor. After a temperature of 220 ° C and a pressure of 105 bar was reached, the oxidation was carried out by blowing air in for 20 minutes. The energy released by the oxidation made it possible to significantly reduce the volume of liquid through evaporation - under the conditions mentioned it is possible to selectively burn the organic products in the black liquor. Lignin, hemicelluloses, resins and sugar were burnt, but the carboxylic acids remain in unburned form as sodium salts in solution in the following composition. After stripping the carbon dioxide, this solution is subjected to causticization, the sodium carbonates being converted into sodium hydroxide, the sodium salts of the carboxylic acids being retained as such. After the precipitated calcium carbonate has been separated off, sodium hydroxide and water are added to the remaining solution until the free sodium hydroxide content reaches the cooking liquor concentration and is fed to the cellulose cooking process. The total loss of alkali remains less than 5%.
  • the solution After stripping the carbon dioxide, caustifying and removing the calcium carbonate, the solution is evaporated to a solids content of 38.5%. By Cooling to 20 ° C, crystallize, calculated on 100 g of green liquor, 13.0 g of sodium acetate trihydrate.
  • Fresh sodium hydroxide solution and water are added to the mother liquor to be returned to the cooking process.
  • the total loss remains less than 8%, the amount of alkali contained in the isolated sodium acetate is of course not taken into account.
  • the mixture of filtrate and wash water was introduced into the oxidation reactor without the resins and the hemicelluloses having been separated beforehand. After a temperature of 220 ° C and a pressure of 155 bar was reached. the oxidation was carried out by blowing in air for 20 minutes. The energy released by the oxidation allowed the volume of liquid to be reduced by evaporation.
  • the composition of the oxidized solution is:
  • Example 2 Sodium carbonate 5.4, After stripping the carbon dioxide and caustifying, the solution containing sodium acetate and sodium hydroxide solution is adjusted to the concentration required for the cooking process and recycled. As soon as sufficient sodium acetate is present in the circuit, the crystallization of the sodium acetate trihydrate can begin, as shown in Example 2.
  • Another part of organic components such as hemicelluloses and resins could be separated by ultrafiltration.
  • Example 1 5.5 g of acetic acid per 100 g of solution are added to the oxidized solution of Example 1 (green liquor), and the mixture is then boiled to remove carbon dioxide.
  • the sodium aceta solution now present (15.8% by weight) is cleaned of small amounts of by-products, then broken down into acetic acid and sodium hydroxide solution by electrodialysis, possibly by membrane electrolysis. After ice division, the sodium hydroxide solution is returned to the concentration required in the cooking process, and acetic acid is only partially returned to the preparation process. The rest corresponds to the amount formed during the cooking process and oxidation, i.e. 6.2 g glacial acetic acid per 100 g green liquor and is available.

Landscapes

  • Paper (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

Pour récupérer des produits chimiques inorganiques à partir des liqueurs résiduaires de procédés de fabrication de la cellulose, on propose de séparer les produits alcalins ou alcalino-terreux des composés organiques par une oxydation partielle ou totale en phase aqueuse avec de l'air et/ou de l'oxygène. Avant cette oxydation, il est possible de séparer la lignine présente dans la liqueur noire par acidification et précipitation avec un acide minéral et de séparer des résines par extraction et les hémicelluloses par ultrafiltration, à la suite de quoi les substances organiques résiduelles encore présentes dans la solution sont oxydées. Il est possible d'opérer l'oxydation par voie humide de telle manière que les acides carboxyliques, en particulier l'acide acétique, ne soient pas brûlés et soient séparés par cristallisation après la caustification. La solution de produits chimiques ainsi libérée de ces substances organiques peut être transformée à nouveau en liqueur par caustification et mise à disposition dans le circuit de production de la cellulose.
EP93911419A 1992-05-05 1993-04-30 Procede de recuperation de produits chimiques de cuisson a partir de la liqueur noire dans la fabrication de la cellulose selon le procede organosolver Expired - Lifetime EP0593744B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CH1435/92 1992-05-05
CH143592A CH687393A5 (de) 1992-05-05 1992-05-05 Kochchemikalienrueckgewinnungsverfahren aus der Schwarzlauge der Zellstoffherstellung.
PCT/CH1993/000109 WO1993022490A1 (fr) 1992-05-05 1993-04-30 Procede de recuperation de produits chimiques de cuisson a partir de la liqueur noire dans la fabrication de la cellulose selon le procede organosolver

Publications (2)

Publication Number Publication Date
EP0593744A1 true EP0593744A1 (fr) 1994-04-27
EP0593744B1 EP0593744B1 (fr) 1998-12-23

Family

ID=4210403

Family Applications (1)

Application Number Title Priority Date Filing Date
EP93911419A Expired - Lifetime EP0593744B1 (fr) 1992-05-05 1993-04-30 Procede de recuperation de produits chimiques de cuisson a partir de la liqueur noire dans la fabrication de la cellulose selon le procede organosolver

Country Status (5)

Country Link
EP (1) EP0593744B1 (fr)
AU (1) AU4038293A (fr)
CH (1) CH687393A5 (fr)
DE (1) DE59309242D1 (fr)
WO (1) WO1993022490A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012117161A1 (fr) 2011-02-28 2012-09-07 Aalto University Foundation Procédé de récupération de produits chimiques

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FI95159C (fi) * 1994-02-11 1995-12-27 Valtion Teknillinen Menetelmä ja laite selluloosakuitujen erottamiseksi ligniinistä
US5565616A (en) * 1994-05-09 1996-10-15 Board Of Regents, The University Of Texas System Controlled hydrothermal processing
US5578647A (en) * 1994-12-20 1996-11-26 Board Of Regents, The University Of Texas System Method of producing off-gas having a selected ratio of carbon monoxide to hydrogen

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3212767A1 (de) * 1982-04-06 1983-10-06 Nicolaus Md Verwaltungsges Verfahren und reaktor zum kontinuierlichen aufschliessen von pflanzenfasermaterial
DE3339449A1 (de) * 1983-10-31 1985-05-09 MD Verwaltungsgesellschaft Nicolaus GmbH & Co. KG, 8000 München Verfahren zur gewinnung von lignin aus alkalischen lignin-loesungen
CA1267648A (fr) * 1985-11-05 1990-04-10 Raphael Katzen Methode de recuperation de la lignine

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9322490A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012117161A1 (fr) 2011-02-28 2012-09-07 Aalto University Foundation Procédé de récupération de produits chimiques

Also Published As

Publication number Publication date
AU4038293A (en) 1993-11-29
WO1993022490A1 (fr) 1993-11-11
DE59309242D1 (de) 1999-02-04
EP0593744B1 (fr) 1998-12-23
CH687393A5 (de) 1996-11-29

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