FI89814B - FOERFARANDE FOER BLEKNING AV CELLULOSAMASSA - Google Patents

FOERFARANDE FOER BLEKNING AV CELLULOSAMASSA Download PDF

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Publication number
FI89814B
FI89814B FI900549A FI900549A FI89814B FI 89814 B FI89814 B FI 89814B FI 900549 A FI900549 A FI 900549A FI 900549 A FI900549 A FI 900549A FI 89814 B FI89814 B FI 89814B
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Prior art keywords
pulp
treatment
enzyme
alkali
bleaching
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FI900549A
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Finnish (fi)
Swedish (sv)
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FI89814C (en
FI900549A0 (en
FI900549A (en
Inventor
Marja Vaheri
Kimmo Ruohoniemi
Hannu Sonni
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Enso Gutzeit Oy
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Application filed by Enso Gutzeit Oy filed Critical Enso Gutzeit Oy
Priority to FI900549A priority Critical patent/FI89814C/en
Publication of FI900549A0 publication Critical patent/FI900549A0/en
Priority to PCT/FI1991/000033 priority patent/WO1991011553A1/en
Priority to AT91903684T priority patent/ATE128498T1/en
Priority to ES91903684T priority patent/ES2079062T5/en
Priority to CA002075187A priority patent/CA2075187A1/en
Priority to JP3503752A priority patent/JPH05509362A/en
Priority to EP91903684A priority patent/EP0513140B2/en
Priority to DE69113444T priority patent/DE69113444D1/en
Publication of FI900549A publication Critical patent/FI900549A/en
Publication of FI89814B publication Critical patent/FI89814B/en
Publication of FI89814C publication Critical patent/FI89814C/en
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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
    • D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
    • D21C5/005—Treatment of cellulose-containing material with microorganisms or enzymes
    • 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
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/1057—Multistage, with compounds cited in more than one sub-group D21C9/10, D21C9/12, D21C9/16
    • 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
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/12—Bleaching ; Apparatus therefor with halogens or halogen-containing compounds
    • D21C9/14—Bleaching ; Apparatus therefor with halogens or halogen-containing compounds with ClO2 or chlorites
    • D21C9/142—Bleaching ; Apparatus therefor with halogens or halogen-containing compounds with ClO2 or chlorites with ClO2/Cl2 in a multistage process involving ClO2/Cl2 exclusively
    • 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
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/147—Bleaching ; Apparatus therefor with oxygen or its allotropic modifications
    • 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
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/16—Bleaching ; Apparatus therefor with per compounds
    • D21C9/163—Bleaching ; Apparatus therefor with per compounds with peroxides

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Chemical & Material Sciences (AREA)
  • Biochemistry (AREA)
  • Microbiology (AREA)
  • Paper (AREA)
  • Investigating Or Analysing Biological Materials (AREA)
  • Hard Magnetic Materials (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention relates to a process for the bleaching of chemical pulp, process which comprises one or several oxidation steps and one or several alkali treatment steps and in which the pulp is treated with an enzyme. The essential idea of the invention is that the pulp is treated with an enzyme in two or more different steps of the process, an oxidation and/or alkali treatment being most preferably carried out between the enzyme treatment steps. The oxidizing chemical used is most preferably oxygen, although peroxide and/or chlorine and/or chlorine dioxide can also be used in addition to or instead of it, and in the enzyme treatment steps, which preferably number 2-4, the same enzyme or alternatively two or more different enzymes may be used. By the enzyme treatment according to the invention, the amount of toxic organic compounds inthe bleaching effluent is decreased and at the same time the chemical oxygen consumption of the effluent is decreased.

Description

! 8 9 814! 8 9 814

Menetelmä selluloosamassan valkaisemiseksi - Förfarande för blekning av cellulosamassa 5 Tämän keksinnön kohteena on menetelmä selluloosamassan valkaisemiseksi, joka menetelmä käsittää ainakin yhden hapetusvaiheen ja ainakin yhden alkalikäsittelyvaiheen ja jossa menetelmässä massaa käsitellään entsyymillä.The present invention relates to a process for bleaching cellulose pulp, which process comprises at least one oxidation step and at least one alkali treatment step, in which the pulp is treated with an enzyme.

10 Varsinkin sulfaattikeitolla saatu selluloosamassa on väril tään ruskeaa, mikä johtuu pääasiassa massassa jäljellä olevasta ligniinistä. Ligniiniä poistetaan valkaisulla, joka on yleensä useampivaiheinen prosessi, jossa massa käsitellään vuorotellen hapettavilla, ligniiniä hajottavilla 15 kemikaaleilla ja hajoamistuloksena syntyviä aineita liuottavilla kemikaaleilla. Eniten käytettyjä hapetuskemikaaleja ovat olleet klooripitoiset aineet sekä happi, kun taas hajoamistuotteita poistavina kemikaaleina on käytetty alka-liliuoksia.10 In particular, the cellulose pulp obtained by sulphate soup is brown in color, mainly due to the lignin remaining in the pulp. Lignin is removed by bleaching, which is usually a multi-step process in which the pulp is treated alternately with oxidizing, lignin-degrading chemicals and solubilizing chemicals. The most widely used oxidizing chemicals have been chlorine-containing substances as well as oxygen, while alkali solutions have been used as decomposition chemicals.

2020

Klooria sisältävät valkaisukemikaalit muuttavat reagoidessaan massan sisältämää ligniiniä orgaanisiksi klooriyhdisteiksi, jotka joutuvat massasta poistuvaan valkaisujäteveteen. Valkaisujätevedet ovat ympäristönsuojelulle ongelma 25 veteen joutuvien orgaanisten klooriyhdisteiden mahdollisen myrkyllisyyden vuoksi, ja myös kemiallisen hapenkulutuksen arvot valkaisujätevesissä ovat haitallisen korkeat.Chlorine-containing bleaching chemicals react to convert the lignin in the pulp to organic chlorine compounds, which end up in the bleaching effluent leaving the pulp. Bleaching effluents are a problem for environmental protection due to the potential toxicity of organochlorine compounds in water, and the values of chemical oxygen demand in bleaching effluents are also harmfully high.

Ympäristöä pahimmin kuormittavat valkaisujätevedet syntyvät 30 valkaisun ensimmäistä kloorausta ja ensimmäistä alkalivai-hetta seuraavissa pesuvaiheissa. Kuormitusta on pyritty alentamaan eri menetelmillä, kuten korvaamalla kloorikaasua klooridioksidilla tai käyttämällä happea ensimmäisen val-kaisuvaiheen hapettavana kemikaalina. Kuitenkaan näillä 35 keinoilla ei ole päästy täysin tyydyttäviin tuloksiin.The most environmentally damaging bleaching effluents are generated in the washing steps following the first 30 chlorination and the first alkali stages of bleaching. Efforts have been made to reduce the load by various methods, such as replacing chlorine gas with chlorine dioxide or using oxygen as the oxidizing chemical in the first bleaching stage. However, these 35 means have not yielded completely satisfactory results.

Kloorifenolien ja muiden myrkyllisten klooriyhdisteiden määrää jätevedessä on tosin onnistuttu vähentämään, mutta veden kemiallisen hapenkulutuksen arvoja ei ole saatu ale- 2 8 9 P 1 4 nemaan riittävästi. Näin ollen mainittujen menetelmien tueksi on tarvittu tehokas biologinen puhdistus.Although the amount of chlorophenols and other toxic chlorine compounds in wastewater has been reduced, the values of the chemical oxygen demand of water have not been sufficiently reduced. Thus, effective biological purification is needed to support these methods.

Viimeaikaisissa tutkimuksissa on havaittu, että käyttämällä 5 valkaisussa apuna entsyymejä on mahdollista irrottaa ligniiniä ja/tai hemiselluloosaa selluloosasta ja tehdä massa tällä tavoin helpommin vaalenevaksi seuraavissa valkaisuvai-heissa. FI-patenttihakemuksen 881192 mukaan entsyymikäsitte-lyllä saadaan myös kloorikemikaaleilla valkaistun massan 10 jäännösklooripitoisuus alenemaan. Entsyymikäsittely on tällöin esitetty suoritettavaksi joko ennen valkaisun hapetus- ja alkalivaiheita tai niiden jälkeen.Recent studies have found that by using enzymes as an aid to bleaching, it is possible to remove lignin and / or hemicellulose from the cellulose and thus make the pulp more easily bleached in subsequent bleaching steps. According to FI patent application 881192, the enzyme treatment also reduces the residual chlorine content of the pulp 10 bleached with chlorine chemicals. The enzyme treatment is then proposed to be performed either before or after the oxidation and alkali steps of bleaching.

Tämän keksinnön tarkoituksena on muodostaa uusi massan 15 entsyymikäsittelyyn perustuva ratkaisu, jolla massa on valkaistavissa siten, että valkaisukemikaalien tarve alenee ja samalla valkaisujäteveden kemiallinen hapenkulutus ja myrkyllisyys vähenevät niin, että veden puhdistustarve jää pienemmäksi. Tunnusomaista keksinnölle on se, että massaa 20 käsitellään entsyymillä valkaisuprosessin kahdessa tai useammassa eri vaiheessa siten, että kussakin entsyymikäsit-telyvaiheessa massa saa oleellisesti erilaisen käsittelyn kuin välittömästi edeltävässä tai seuraavassa prosessin vaiheessa.The object of the present invention is to provide a new solution based on enzyme treatment of pulp 15, with which the pulp can be bleached so that the need for bleaching chemicals is reduced and at the same time the chemical oxygen demand and toxicity of the bleaching effluent are reduced. The invention is characterized in that the pulp 20 is treated with an enzyme in two or more different steps of the bleaching process, so that in each enzymatic treatment step the pulp receives a substantially different treatment than in the immediately preceding or following step of the process.

2525

Keksinnön mukaan on siis havaittu, että entsyymien vaikutus tehostuu, kun niitä käytetään useammassa eri vaiheessa, sopivimmin prosessiin kuuluvien hapetus- ja alkalivaiheiden väleillä. Kun valkaisuprosessin alussa suoritetun entsyymi-30 käsittelyn on todettu mahdollistavan käytettävien kloorike- mikaalien määrän vähentämisen noin 25 %:lla, päästään keksinnön mukaisilla toistetuilla entsyymikäsittelyillä huomattavasti suurempaan valkaisukemikaalien säästöön.Thus, according to the invention, it has been found that the action of the enzymes is enhanced when they are used in several different steps, preferably between the oxidation and alkali steps involved in the process. When the enzyme-30 treatment carried out at the beginning of the bleaching process has been found to reduce the amount of chlorine chemicals used by about 25%, the repeated enzyme treatments according to the invention achieve considerably greater savings in bleaching chemicals.

35 Tarkoituksenmukainen entsyymikäsittelyvaiheiden määrä keksinnön mukaisessa valkaisuprosessissa on kahdesta neljään.The appropriate number of enzyme treatment steps in the bleaching process of the invention is from two to four.

Eräs edullinen prosessi, johon kuuluu kolme entsyymikäsitte-lyvaihetta, käsittää ensimmäisenä vaiheena keitosta saadun s 9 I J.A preferred process comprising three enzyme treatment steps comprises, as a first step, s 9 I J obtained from the cooking.

3 massan entsyymikäsittelyn ja seuraavina vaiheina massan hapetuksen hapettavalla kemikaalilla, toisen entsyymikäsittelyn, käsittelyn alkalilla ja kolmannen entsyymikäsittelyn mainitussa järjestyksessä. Näiden vaiheiden jälkeen massan 5 valkaisu voi vielä jatkua yhdessä tai useammassa hapetus- ja/tai alkalikäsittelyvaiheessa.3 enzyme treatment of the pulp and subsequent steps of oxidation of the pulp with an oxidizing chemical, a second enzyme treatment, an alkali treatment and a third enzyme treatment in that order. After these steps, the bleaching of the pulp 5 can still continue in one or more oxidation and / or alkali treatment steps.

Haitallisten orgaanisten klooriyhdisteiden määrän minimoimiseksi jätevesissä ja saatavassa valkaistussa selluloosamas-10 sassa on edullista käyttää prosessin hapetusvaiheissa happea ja/tai vetyperoksidia ja/tai klooridioksidia. Näin menetellen saadaan orgaanisten klooriyhdisteiden määrää jätevedessä alennetuksi yli 90 %:lla myös havupuumassan valkaisussa, mikä tähänastisin tunnetuin menetelmin on ollut mahdotonta.In order to minimize the amount of harmful organochlorine compounds in the effluent and the resulting bleached cellulose pulp, it is preferred to use oxygen and / or hydrogen peroxide and / or chlorine dioxide in the oxidation steps of the process. In this way, the amount of organochlorine compounds in the wastewater can be reduced by more than 90% also in the bleaching of softwood pulp, which has been impossible with the methods known so far.

1515

Keksinnön erään edullisen sovellutusmuodon mukaan ainakin yhtä entsyymikäsittelyvaihetta seuraa prosessissa käsittely alkalilla, jossa alkalin ohella käytetään hapettavaa kemikaalia, kuten happea tai peroksidia. Tällaisen hapettavan 20 alkalikäsittelyn on todettu erityisen tehokkaasti alentavan kloorikemikaalien tarvetta valkaisussa.According to a preferred embodiment of the invention, at least one enzyme treatment step is followed in the process by treatment with an alkali in which an oxidizing chemical, such as oxygen or peroxide, is used in addition to the alkali. Such oxidative alkali treatment has been found to be particularly effective in reducing the need for chlorine chemicals in bleaching.

Keksinnön mukaisessa valkaisuprosessissa entsyymikäsittelyt pilkkovat massan sisältämää hemiselluloosaa ja/tai ligniiniä 25 ja tekevät massan huokoisemmaksi, mikä lisää kemikaalien tehoa seuraavissa massan käsittelyvaiheissa. Entsyymikäsit-telyä voi seurata massan pesu, joka poistaa massasta pilkkoutuneita aineksia, jotka voidaan johtaa polttoon niin, ettei niistä aiheudu minkäänlaista jätevesikuormitusta vaan 30 niiden sisältämä energia saadaan hyödynnetyksi tehtaan energiahuollossa.In the bleaching process of the invention, the enzyme treatments cleave the hemicellulose and / or lignin contained in the pulp and make the pulp more porous, which increases the effectiveness of the chemicals in the subsequent pulp processing steps. The enzyme treatment can be followed by the washing of the pulp, which removes the decomposed materials from the pulp, which can be led to incineration so that they do not cause any wastewater load, but the energy contained in them is utilized in the energy supply of the plant.

Entsyymikäsittelyvaiheita lukuunottamatta keksinnön mukainen massan valkaisu voi tapahtua tavanomaiseen tapaan siten, 35 että hapetus- ja alkalivaiheet vuorottelevat. Eri vaiheiden jälkeen massa voidaan pestä valkaisukemikaalien ja pilkkoutuneiden aineosien poistamiseksi.With the exception of the enzyme treatment steps, the pulp bleaching according to the invention can take place in a conventional manner, with the oxidation and alkali steps alternating. After the various steps, the pulp can be washed to remove bleaching chemicals and degraded ingredients.

, b 9 8 1 4 4, b 9 8 1 4 4

Entsyyxnikäsittely tapahtuu keksinnön mukaan edullisesti lämpötila-alueella 10-90°C, sopiviimoin alueella 40-80°C, ja pH:ssa 3,0-11,0, sopivimmin 4,0-10,0. Käytetty entsyymi voi olla hemisellulaasi, sellulaasi, pektinaasi, esteraasi, 5 ligninaasi, fenolioksidaasi tai näiden seos. Hemisellulaasit sekä fenolioksidaaseihin kuuluva lakkaasi ovat erityisen sopivia.According to the invention, the enzyme treatment preferably takes place in the temperature range from 10 to 90 ° C, preferably in the range from 40 to 80 ° C, and at a pH of 3.0 to 11.0, most preferably 4.0 to 10.0. The enzyme used may be hemicellulase, cellulase, pectinase, esterase, ligninase, phenol oxidase or a mixture thereof. Hemicellulases as well as laccase, which is a phenol oxidase, are particularly suitable.

Keksinnön mukaiseen prosessiin kuuluvissa entsyymikäsittely-10 vaiheissa on mahdollista käyttää yhtä ja samaa entsyymiä, kuten hemisellulaasia. Mahdollista on myös, että prosessiin kuuluu ainakin kaksi erillistä entsyymikäsittelyvaihetta, joissa käytetään ainakin kahta eri entsyymiä. Prosessi voi siten alkaa esimerkiksi hemisellulaasikäsittelyllä, jota 15 hapetusvaiheen jälkeen seuraa lakkaasikäsittely ja seuraavan alkalivaiheen jälkeen toinen hemisellulaasikäsittely. Eri entsyymejä käytettäessä voivat entsyymikäsittelyt myös tapahtua prosessissa peräkkäin.In the enzyme treatment steps of the process according to the invention, it is possible to use the same enzyme, such as hemicellulase. It is also possible that the process comprises at least two separate enzyme treatment steps using at least two different enzymes. The process can thus start, for example, with a hemicellulase treatment, followed by a laccase treatment after the oxidation step and a second hemicellulase treatment after the next alkali step. When different enzymes are used, the enzyme treatments can also take place in the process sequentially.

20 Keksintöä selostetaan seuraavassa lähemmin laboratoriokokeisiin perustuvan suoritusesimerkin avulla.The invention will now be described in more detail by means of an embodiment based on laboratory experiments.

Esimerkki 300 g saan mäntysulfaattikeitosta saatua massakuiva-ainetta 25 (massan kuiva-ainepitoisuus 30 %) lisättiin laimennettua entsyymiseosta Pulpzyme (Novo, hemisellulaasi) siten, että seoksen sakeudeksi tuli 10 % ja ksylanaasiaktiivisuudeksi 5 U/g massan kuiva-ainetta. Tätä ennen massan pH oli säädetty etikkahapolla tasolle 5,5-6,0. Entsyymikäsittelyn lämpö-30 tila oli 55°C ja käsittelyaika 2 h.Example 300 g of pulp dry matter 25 obtained from pine sulphate soup (pulp dry matter content 30%) was added to a diluted enzyme mixture Pulpzyme (Novo, hemicellulase) so that the mixture had a consistency of 10% and a xylanase activity of 5 U / g pulp dry matter. Prior to this, the pH of the pulp was adjusted to 5.5-6.0 with acetic acid. The heat-30 state of the enzyme treatment was 55 ° C and the treatment time was 2 h.

Entsyymikäsittelyn jälkeen massa pestiin vedellä.After the enzyme treatment, the pulp was washed with water.

Seuraavaksi massalle suoritettiin hapettava valkaisukäsitte-35 ly käyttäen seosta, joka sisälsi 50 % klooridioksidia ja 50 % kloorikaasua. Seosta annosteltiin määrä, joka oli 2,0 x massan keiton jälkeinen kappaluku. Käsittelylämpötila oli 40°C ja käsittelyaika 45 min ja massan sakeus 3,5 %.The pulp was then subjected to an oxidative bleaching treatment using a mixture of 50% chlorine dioxide and 50% chlorine gas. The mixture was metered in an amount of 2.0 x the number of pieces after cooking the pulp. The treatment temperature was 40 ° C and the treatment time was 45 min and the consistency of the pulp was 3.5%.

li 5 b 9 Γ 1 4li 5 b 9 Γ 1 4

Seuraavaksi massalle suoritettiin alkalikäsittely käyttäen 2-%:ista natriumhydroksidiliuosta, jonka annos oli 0,9 x kappa. Seoksen sakeus oli 10 %, ja käsittelylämpötila oli 5 60°C ja käsittelyaika 90 min. Alkalikäsittelyn jälkeen massa pestiin 20-kertaisella vesimäärällä.The pulp was then subjected to alkali treatment using 2% sodium hydroxide solution at a dose of 0.9 x kappa. The consistency of the mixture was 10% and the treatment temperature was 60 ° C and the treatment time was 90 min. After alkali treatment, the pulp was washed with 20 times the amount of water.

Tämän jälkeen valkaisua jatkettiin toistamalla entsyymivaihe käyttäen samaa entsyymiseosta kuin ensimmäisessä vaiheessa 10 ja hapetusvaihe käyttäen klooridioksidia sekä pesemällä massa vaiheiden välillä siten kuin edellä on esitetty.Bleaching was then continued by repeating the enzyme step using the same enzyme mixture as in the first step 10 and the oxidation step using chlorine dioxide and washing the pulp between the steps as described above.

Tällöin entsyymin määrä toisessa entsyymikäsittelyssä oli 2,5 U/g massaa. Klooridioksidin määrä toisessa hapetusvai-heessa oli 1,5 % valkaistavan massan määrästä.In this case, the amount of enzyme in the second enzyme treatment was 2.5 U / g mass. The amount of chlorine dioxide in the second oxidation step was 1.5% of the amount of pulp to be bleached.

1515

Valkaistu massa analysoitiin. Tulokset on esitetty seuraa-vassa taulukossa 1.The bleached pulp was analyzed. The results are shown in Table 1 below.

Edellä kuvatun keksintöä valaisevan kokeen (koe 2) lisäksi 20 suoritettiin vertailukoe (koe 1), jonka tulokset on niin ikään esitetty seuraavassa taulukossa 1.In addition to the experiment (Experiment 2) illustrating the invention described above, a comparative experiment (Experiment 1) was performed, the results of which are also shown in the following Table 1.

Kokeet suoritettiin seuraavasti:The experiments were performed as follows:

Koe 1 (vertailukoe): massalle ei suoritettu toista entsyymi-25 käsittelyä. Muilta osin koe vastasi edellä esitettyä (koe 2).Experiment 1 (comparative experiment): the pulp was not subjected to a second enzyme-25 treatment. In other respects, the experiment corresponded to the above (Experiment 2).

6 b 9 8 1 46 b 9 8 1 4

Taulukko 1table 1

Koe 1 Koe 2 (vertailu) 5 I entsyymikäsittely 1 1 - entsyymiannos (1/t)Experiment 1 Experiment 2 (comparison) 5 I enzyme treatment 1 1 - enzyme dose (1 / h)

ClOa/Cl-suhde 50/50 50/50 10 Kappa 27,7 27,7ClOa / Cl ratio 50/50 50/50 10 Kappa 27.7 27.7

PHPH

- entsyymivaihe 5,4 5,6 - hapetusvaihe (ClOa/Cl) 2,1 2,1 15 - Alkalivaihe 11/7 11,6- enzyme step 5.4 5.6 - oxidation step (ClOa / Cl) 2.1 2.1 15 - Alkali step 11/7 11.6

Aktiivisen kloorin kulutus (%) 5,54 5,54 20 Välikappa 5,7 5,7 II entsyymikäsittely - 0,5 (1/t)Consumption of active chlorine (%) 5.54 5.54 20 Intermediate 5.7 5.7 II enzyme treatment - 0.5 (1 / h)

25 pH25 pH

- II entsyymivaihe 5,3 - hapetusvaihe (C10a) 2,1 2,1 - SO2 vaihe alku/loppu 4,8/3,7 4,8/3,7 30 Vaaleus (ISO) 60,97 67,54- Enzyme step II 5.3 - oxidation step (C10a) 2.1 2.1 - SO2 step start / end 4.8 / 3.7 4.8 / 3.7 30 Brightness (ISO) 60.97 67.54

Alan ammattimiehelle on selvää, että keksinnön erilaiset 35 sovellutusmuodot eivät rajoitu edellä esitettyihin esimerk keihin vaan voivat vaihdella oheisten patenttivaatimusten puitteissa.It will be apparent to those skilled in the art that the various embodiments of the invention are not limited to the examples set forth above but may vary within the scope of the appended claims.

IlIl

Claims (8)

1. Förfarande för blekning av cellulosamassa, bestäende av ätminstone ett oxidationsskede och ätminstone ett aikaiibe- 5 handlingsskede och i vilket förfarande massan behandlas med enzym vid blekningsprocessens tvä eller flera olika skeden, kännetecknat av att vid enzymbehandlingsskedet massan fär väsentligen olik behandling än vid det omedelbart föregäende eller följande processkedet· 10A process for bleaching cellulose pulp, consisting of at least one oxidation stage and at least one acai treatment stage, in which process the pulp is treated with enzyme at the two or more different stages of the bleaching process, characterized in that at the enzyme treatment stage the pulp receives substantially different treatment than at the instant. previous or subsequent process stage · 10 2. Förfarande enligt krav 1, kännetecknat av att det första skedet vid blekningsprocessen bestär av mas-sans enzymbehandling och att följande skeden omfattar massans oxidation med en oxiderande kemikalie, den andra enzymbehand- 15 lingen, behandlingen med alkali, och den tredje enzymbehand-lingen i nämnda ordning, varefter blekningen av massan ännu fortsätts vid ett eller flera oxidations- och/eller alkali-behandlingsskeden. 20Process according to claim 1, characterized in that the first stage of the bleaching process consists of the pulp enzyme treatment and the following stage comprises the oxidation of the pulp with an oxidizing chemical, the second enzyme treatment, the alkali treatment, and the third enzyme treatment. in said order, after which the bleaching of the pulp is still continued at one or more oxidation and / or alkali treatment stages. 20 3. Förfarande enligt krav 1 eller 2, kännetecknat av att som den oxiderande kemikalien används syre vid ett eller flera processkeden.Process according to claim 1 or 2, characterized in that as the oxidizing chemical oxygen is used at one or more process stages. 4. Förfarande enligt nägot av föregäende krav, k ä n n e -25 tecknat av att ätminstone ett enzymbehandlingsskede följs vid processen av behandlingen med alkali, varvid för-utom alkali används en oxiderande kemikalie, som syre eller peroxid. 30 5. Förfarande enligrt krav 2-3, kännetecnat av att det första processkedet bestär av en enzymbehandling och att följande skeden omfattar oxidation med syre, den andra enzymbe- handlingen, behandlingen med alkali, vid vilken förutom al-35 kali används syre eller peroxid, den tredje enzymbehandlin- H 9 f; 1 4 ίο gen, oxidation med syre eller klordioxid, behandling med alkali och oxidation med syre eller klordioxid, varvid dessa skeden följer varandra i nämnda ordning.4. A process according to any preceding claim, characterized in that at least one enzyme treatment stage is followed in the process of the treatment with alkali, in which, besides alkali, an oxidizing chemical, such as oxygen or peroxide, is used. Process according to claims 2-3, characterized in that the first process stage consists of an enzyme treatment and that the following stages comprise oxidation with oxygen, the second enzyme treatment, the treatment with alkali, in which oxygen or peroxide is used in addition to alkali. , the third enzyme treatment H 9 f; 1 4 gene, oxidation with oxygen or chlorine dioxide, treatment with alkali and oxidation with oxygen or chlorine dioxide, these phases following each other in said order. 55 6. Förfarande enligt nägot av föregäende krav, k ä n n e - tecknat av att som enzym används hemicellulas, cel-lulas, pektinas, esteras, ligninas och/eller fenoloxidas.6. A process according to any preceding claim, characterized in that as the enzyme is used hemicellulase, cellulase, pectinase, esterase, ligninase and / or phenol oxidase. 7. Förfarande enligt nägot av föregäende krav, k ä n n e -tecknat av att tili processen hör ätminstone tvä sepa- 10 rata enzymbehandlingsskeden, vid vika används ätminstone tvä olika enzymer.Process according to any of the preceding claims, characterized in that the process comprises at least two separate enzyme treatment stages, at least two different enzymes are used. 8. Förfarande enligt nägot av föregäende krav, k ä n n e -tecknat av att med förfarandet bleks massan som fäs av 15 barrträ, säsom tallsulfatmassa. I:8. A process according to any of the preceding claims, characterized in that the process is bleached with the pulp, which is made of softwood, such as pine sulfate pulp. IN:
FI900549A 1990-02-02 1990-02-02 FOERFARANDE FOER BLEKNING AV CELLULOSAMASSA FI89814C (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
FI900549A FI89814C (en) 1990-02-02 1990-02-02 FOERFARANDE FOER BLEKNING AV CELLULOSAMASSA
DE69113444T DE69113444D1 (en) 1990-02-02 1991-02-01 METHOD FOR BLEACHING CHEMICAL PAPER FIBER.
ES91903684T ES2079062T5 (en) 1990-02-02 1991-02-01 PROCEDURE FOR THE BLEACHING OF CHEMICAL PAPER PASTE.
AT91903684T ATE128498T1 (en) 1990-02-02 1991-02-01 METHOD FOR BLEACHING CHEMICAL PAPER PULP.
PCT/FI1991/000033 WO1991011553A1 (en) 1990-02-02 1991-02-01 A process for the bleaching of chemical pulp
CA002075187A CA2075187A1 (en) 1990-02-02 1991-02-01 Process for the bleaching of chemical pulp
JP3503752A JPH05509362A (en) 1990-02-02 1991-02-01 Chemical pulp bleaching method
EP91903684A EP0513140B2 (en) 1990-02-02 1991-02-01 A process for the bleaching of chemical pulp

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI900549A FI89814C (en) 1990-02-02 1990-02-02 FOERFARANDE FOER BLEKNING AV CELLULOSAMASSA
FI900549 1990-02-02

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FI900549A0 FI900549A0 (en) 1990-02-02
FI900549A FI900549A (en) 1991-08-03
FI89814B true FI89814B (en) 1993-08-13
FI89814C FI89814C (en) 1993-11-25

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EP (1) EP0513140B2 (en)
JP (1) JPH05509362A (en)
AT (1) ATE128498T1 (en)
CA (1) CA2075187A1 (en)
DE (1) DE69113444D1 (en)
ES (1) ES2079062T5 (en)
FI (1) FI89814C (en)
WO (1) WO1991011553A1 (en)

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FI90670C (en) * 1991-05-02 1994-03-10 Metsae Serla Oy Treatment of alkali-treated pulp for use in papermaking
US7816129B2 (en) 1994-07-29 2010-10-19 Ab Enzymes Gmbh Production and secretion of proteins of bacterial origin in filamentous fungi
EP0905306A1 (en) 1997-09-26 1999-03-31 Consortium für elektrochemische Industrie GmbH Multicomponent system for modifying, decomposing or bleaching lignin or lignin-containing materials and method of using this system
WO2000014243A1 (en) 1998-09-04 2000-03-16 University Of Georgia Research Foundation, Inc. Phenolic acid esterases, coding sequences and methods
US6602700B1 (en) 1998-09-04 2003-08-05 University Of Georgia Research Foundation, Inc. Phenolic acid esterases, coding sequences and methods
CA2432788C (en) 2000-12-22 2008-10-07 Iogen Bio-Products Corporation Alkaline extraction stages comprising xylanase
AU2002229430A1 (en) * 2001-01-18 2002-07-30 Iogen Bio-Products Corporation Use of xylanase in pulp bleaching
US7368036B2 (en) * 2002-03-06 2008-05-06 Iogen Bio-Products Corporation Xylanase treatment of chemical pulp
EP1516053B1 (en) 2002-06-14 2012-10-17 Verenium Corporation Xylanases, nucleic adics encoding them and methods for making and using them
EP3406621A1 (en) 2006-02-14 2018-11-28 BP Corporation North America Inc. Xylanases, nucleic acids encoding them and methods for making and using them

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FI90888B (en) * 1989-02-14 1993-12-31 Enso Gutzeit Oy Method for bleaching cellulose pulp
ZA904441B (en) * 1989-06-22 1991-03-27 Int Paper Co Enzymatic delignification of lignocellulosic material

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Publication number Publication date
FI89814C (en) 1993-11-25
ATE128498T1 (en) 1995-10-15
DE69113444D1 (en) 1995-11-02
FI900549A0 (en) 1990-02-02
ES2079062T5 (en) 1998-07-16
WO1991011553A1 (en) 1991-08-08
EP0513140B2 (en) 1998-03-18
CA2075187A1 (en) 1991-08-03
EP0513140A1 (en) 1992-11-19
EP0513140B1 (en) 1995-09-27
JPH05509362A (en) 1993-12-22
FI900549A (en) 1991-08-03
ES2079062T3 (en) 1996-01-01

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