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EP0593744B1 - 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 Download PDF

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Publication number
EP0593744B1
EP0593744B1 EP93911419A EP93911419A EP0593744B1 EP 0593744 B1 EP0593744 B1 EP 0593744B1 EP 93911419 A EP93911419 A EP 93911419A EP 93911419 A EP93911419 A EP 93911419A EP 0593744 B1 EP0593744 B1 EP 0593744B1
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EP
European Patent Office
Prior art keywords
oxidation
process according
digesting
liquor
lignin
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
EP93911419A
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German (de)
English (en)
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EP0593744A1 (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
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Granit SA
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Publication date
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    • 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 pulp production by partial or complete wet oxidation of the organic components with air and or or oxygen.
  • the lignin, resin, and hemicellulose extracts that result from the pulp production have been burned in the recovery boiler after their concentration in order to generate energy, but above all to recover the inorganic cooking chemicals and feed them back into the cooking process.
  • a direct discharge of the cooking waste liquor into the receiving water is not possible for ecological reasons.
  • the combustion processes are complicated, risky and represent a large investment for the pulp factories, which in turn requires a large production capacity in order to make the pulp production profitable.
  • a number of processes have been proposed which aim to obtain and utilize some of the organic components in the black liquor.
  • the cooking liquors also contain considerable amounts of carboxylic acids as alkali salts.
  • the process which forms the subject of the patent allows the organic substances contained in cooking liquors to be partially or completely oxidized.
  • the oxidation takes place in the aqueous phase with air, oxygen or mixtures of these two, under pressure and at elevated temperature.
  • This so-called wet oxidation is carried out in batch or continuous mode in a reactor (5) with thorough mixing, at pressures of 20 to 300 bar and at a temperature of 150 to 350 ° C, with the introduction of the oxidizing agent (6) for 1 to 60 Minutes.
  • 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 organic acids (9).
  • the salts of the organic acids for example sodium acetate
  • crystallization (10) after cooling, the sodium hydroxide solution remaining in solution.
  • the sodium hydroxide solution is returned to the pulp cooking process with portions of sodium acetate.
  • the sodium acetate is available as a sales product or can be broken down into sodium hydroxide solution and acetic acid by known processes such as membrane electrolysis.
  • 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 from an organosolv process for the production of pulp, after the organic has been separated off Solvent applied, after or before the separation of the lignins (1,2), the hemicelluloses and the resins (3,4).
  • the green liquor After several repetitions of the cycle described in Example 1, after oxidation, the green liquor reaches the following composition: water 78.2% Carbon dioxide 1.5% Sodium acetate 15.7% Sodium carbonate 4.6%
  • 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.
  • Black liquor of the same composition as in Example 1 was heated to 65 ° C and gassed with flue gas containing 12% CO 2 with vigorous stirring. After a pH of 7.8 was reached, the precipitated lignin was separated off by filtration and washed. 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 air in 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: water 89.5% Carbon dioxide 1.3% Sodium acetate 3.8% 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 be started, as shown in Example 2.
  • DOC dissolved form

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

Claims (8)

  1. Procédé de récupération des produits chimiques inorganiques de digestion de la liqueur de digestion provenant de la production de cellulose par des procédés Organosolv, après séparation des solvants organiques, en trois étapes essentielles qui consistent en l'oxydation partielle ou complète en phase liquide des composés organiques par de l'air, de l'oxygène ou un mélange des deux, la caustification de la liqueur oxydée par de l'oxyde de calcium pour la conversion du carbonate de calcium en soude caustique, et la séparation d'acétate de sodium par cristallisation.
  2. Procédé selon la revendication 1, caractérisé par le fait que la liqueur de digestion libérée partiellement ou complètement des composés organiques est convertie dans l'hydroxyde correspondant par un procédé de caustification usuel après chauffage en vue de la conversion du bicarbonate en carbonate.
  3. Procédé selon les revendications 1 et 2, caractérisé par le fait que les liqueurs de digestions, qui contiennent des composés organiques en plus des produits chimiques inorganiques de digestion, sont libérées partiellement ou complètement des composés organiques par oxydation humide a) après précipitation de composés de lignine par un acide minéral, en particulier le dioxyde de carbone, ou b) après précipitation de composés de lignine par un acide carboxylique, en particulier l'acide acétique, ou c) sans précipitation de composés de lignine.
  4. Procédé selon les revendications 1 à 3, caractérisé par le fait que l'oxydation en phase liquide est effectuée après séparation de résines par extraction.
  5. Procédé selon les revendications 1 à 4, caractérisé par le fait que l'énergie dégagée par l'oxydation humide des composés organiques est utilisée pour la production de cellulose.
  6. Procédé selon les revendications 1 à 5, caractérisé par le fait que l'oxydation en phase liquide est effectuée dans des conditions de réaction où les acides carboxyliques formés durant l'oxydation, en particulier l'acide acétique, ne sont pas oxydés.
  7. Procédé selon les revendications 1 à 6, caractérisé par le fait que de l'acétate de sodium est cristallisé après la caustification du carbonate de sodium et la solution restante, qui contient de la soude caustique et de l'acétate résiduel, est retournée au procédé de digestion après ajustement de la concentration en produits chimiques adéquate.
  8. Procédé selon les revendications 1 à 7, caractérisé par le fait que l'oxydation en phase liquide est effectuée dans les conditions suivantes:
    a) températures de 150°C à 350°C, de préférence entre 200°C et 320°C,
    b) pressions d'air, d'oxygène ou de mélanges des deux, de 20 à 300 bar, de préférence entre 40 et 250 bar,
    c) temps de résidence dans le réacteur de 1 à 60 minutes, de préférence entre 5 et 15 minutes.
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 EP0593744A1 (fr) 1994-04-27
EP0593744B1 true EP0593744B1 (fr) 1998-12-23

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Family Applications (1)

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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)

Families Citing this family (4)

* 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
FI123086B (fi) 2011-02-28 2012-10-31 Aalto Korkeakoulusaeaetioe Menetelmä kemikaalien talteenottamiseksi

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

Also Published As

Publication number Publication date
WO1993022490A1 (fr) 1993-11-11
EP0593744A1 (fr) 1994-04-27
CH687393A5 (de) 1996-11-29
AU4038293A (en) 1993-11-29
DE59309242D1 (de) 1999-02-04

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