EP0287960B1 - Procédé de fabrication d'un hydrolysat d'hémicellulose et une pâte spéciale - Google Patents

Procédé de fabrication d'un hydrolysat d'hémicellulose et une pâte spéciale Download PDF

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Publication number
EP0287960B1
EP0287960B1 EP88106006A EP88106006A EP0287960B1 EP 0287960 B1 EP0287960 B1 EP 0287960B1 EP 88106006 A EP88106006 A EP 88106006A EP 88106006 A EP88106006 A EP 88106006A EP 0287960 B1 EP0287960 B1 EP 0287960B1
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EP
European Patent Office
Prior art keywords
cooking
prehydrolysis
wood
temperature
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
EP88106006A
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German (de)
English (en)
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EP0287960A2 (fr
EP0287960A3 (fr
Inventor
Panu Tikka
Nils Erik Virkola
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SCITECH SERVICES, INC.
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SciTech Services Inc
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Publication date
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Publication of EP0287960A3 publication Critical patent/EP0287960A3/fr
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Publication of EP0287960B1 publication Critical patent/EP0287960B1/fr
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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
    • D21C3/22—Other features of pulping processes
    • D21C3/222—Use of compounds accelerating the pulping processes
    • C—CHEMISTRY; METALLURGY
    • C13—SUGAR INDUSTRY
    • C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
    • C13K1/00—Glucose; Glucose-containing syrups
    • C13K1/02—Glucose; Glucose-containing syrups obtained by saccharification of cellulosic materials

Definitions

  • the invention relates to a process for the production of a hemicellulose hydrolysate and special pulp having a high content of alpha cellulose, such as dissolving pulp, from a material containing lignocellulose through two steps, the first step comprising the prehydrolysis of the material and the second step the dissolving of the lignin contained in the prehydrolyzed material by means of a cooking liquor comprising sodium sulphite, sodium hydroxide and an anthraquinone.
  • US-A-3 532 597 describes a prehydrolysis-digestion process for preparing dissolving pulp utilizing an alkaline sodium sulphite cooking liquor to which has been added a substantial proportion of sodium, sulphide, optionally some sodium carbonate, and sodium hydroxide.
  • DE-A-2 628 971 describes a prehydrolysis-neutral sulphite process, wherein prior to the sulphite cooking the hydrolysate products are removed by washing. However, it is not possible to produce dissolving pulp by said process.
  • the product produced by the known process is defibrated mechanically to be used in the production of e.g. board.
  • Such additional chemicals used in addition to the basic chemicals of sulphite cooking, include sulphide, white liquor, and antraquinone, see e.g. FI-A-67 104 and US-A-4 213 821. These sulphite cooking variations do not, however, imply hydrolytic conditions.
  • a separate prehydrolysis step is interesting in the view of the fact that it enables the adjustment of the hydrolysis of hemicelluloses as desired by varying the hydrolysis conditions.
  • the prehydrolysis-sulphate process the delignification is not carried out until in a separate second cooking step.
  • the prehydrolysis is carried out either as a water prehydrolysis or in the presence of a catalyst.
  • Organic acids liberated from wood in the water prehydrolysis perform a major part of the process, whereas small amounts of mineral acid or sulphur dioxide, in some cases even sulphite waste liquor, are added to the digester in "assisted" prehydrolysis. It has previously been necessary to effect the lignin dissolving step after the prehydrolysis as sulphate cooking which has several drawbacks.
  • the prehydrolysis-sulphate process has e.g. the following drawbacks:
  • An object of the present invention is to provide an improved process for the production of special pulp having a high content of alpha cellulose, such as dissolving pulp, which gives a high yield of the special pulp to be produced and good delignification.
  • Suitable prehydrolyzing agents include e.g. water, mineral acid, sulphur dioxide, sulphite cooking acid, and sulphite waste liquor.
  • Preferred prehydrolyzing agents include sulphur oxide, sulphuric acid, and water.
  • a suitable prehydrolyzing temperature is 100 to 180 °C, preferably 155 to 170 °C, and a suitable hydrolyzing time is 10 to 200 minutes, preferably 90 to 170 minutes.
  • the material containing lignocellulose preferably consists of softwood or hardwood.
  • the use of the so called neutral sulphite antraquinone cooking process effects a partial ionization of the lignin inactivated in the prehydrolysis, the initial pH being at least 10, e.g. 11 to 12, and that anthraquinone as an additive in the cooking catalyzes the breaking of nucleophilic beta aryl ether bonds, which at the end results in the liberation of fibres, i.e. a successful cooking.
  • sulphite ions in neutral sulphite cooking react simultaneously and participate in the decomposing of the structure of lignin and above all sulphonate the lignin material and fragments which thus become more hydrophilic and dissolve more easily in the cooking liquor, thus contributing to the formation of a successful cooking and to the continuation thereof to a very low content of residual lignin.
  • the prehydrolysis-neutral sulphite anthraquinone process according to the invention not only gives a result as successful as that of the sulphate process but also provides all the advantages typical of sulphite cooking.
  • the increased yield of the process according to the invention is due to the fact that there does not occur splitting of cellulose to any greater degree during the neutral sulphite cooking step.
  • the high alkalinity causes alkaline hydrolysis, and the peeling-off reaction in particular results irrevocably in a yield loss.
  • the process according to the invention enables the recovery of nearly all of the high molecular weight cellulose material originally contained in the wood material.
  • pulp which has undergone neutral sulphite anthraquinone cooking is easy to bleach, i.e. the residual lignin remaining in the fibre after the cooking is easy to remove.
  • the delignification resembles sulphite cooking; the condensation of the structure of lignin is insignificant; and the sulphonation makes lignin more hydrophilic.
  • the residual lignin in sulphate cooking is strongly condensated and the content thereof is on a higher level.
  • the removal of this kind of residual lignin in bleaching requires five to six bleaching steps and plenty of expensive chlorine dioxide.
  • the bleaching of pulp obtained by means of the process according to the invention can be carried out by three steps only and the demand of chemicals, too, is lower.
  • Chips and a prehydrolyzing liquor were metered into a chip basket positioned in a 20-litre forced circulation digester.
  • the cover of the digester was closed and the prehydrolysis was carried out according to the temperature program by heating the digester circulation indirectly by means of steam. After the hydrolysis time had passed, the hydrolysate was removed from the digester and recovered.
  • the prehydrolyzed chip material contained in the digester was washed in the digester for 5 minutes with warm water, the cover was opened, and the chips were passed into a centrifuge in which excess water was removed. The centrifugalized material was weighed and a dry substance sample was taken for determining the hydrolysis loss.
  • the prehydrolyzed chip material was returned to the digester, cooking liquor and anthraquinone were added, the cover was closed, and the cooking was carried out according to the temperature program. At the end of the cooking the cooking liquor was removed rapidly and the digester was filled with cold water, whereafter water was allowed to flow for 10 hours for washing the cooked chip material. After the wash the pulp was disintegrated by means of a wet disintegrator for one minute and assorted with a flat screen plate of 0.35 mm. Shives were recovered and weighed dry for determining the shive content. The accepted fraction was passed into the centrifuge for dewatering, homogenized, and weighed. Laboratory analyses were carried out on this pulp and the pulp was further used in bleaching tests.
  • Prehydrolyzing step Wood amount, g of abs. dry chips 2000 Prehydrolyzing agent SO2 Amount of prehydrolyzing agent, % on dry wood 0.25 Liquor ratio 6:1 Temperature rising time, min 40 Prehydrolysis temperature, °C 155 Prehydrolysis time, min 170 Prehydrolysis loss, % on wood 26.6 Cooking step Na2SO3, % on wood as NaOH 22 Na2CO3, % on wood as NaOH 5 Anthraquinone, % on wood 0.1 Liquor ratio 4.5:1 pH of the cooking liquor 11.3 Rising of the temperature °C/min 1 Cooking temperature, °C 175 Cooking time, min 170 Yield, % on wood 39.3 Kappa number 17.2 Shive content, % on wood 0.1 Properties of O-D-E-D bleached pulp Final yield, % of wood 36.7 ISO brightness 87.1 Alpha cellulose % 94.2 Viscosity, SCAN dm3/kg 764
  • Sulphur dioxide prehydrolysis Cooking step 1 ammonium neutral sulphite cooking Cooking step 2: sulphur dioxide water acidic sulphite cooking Kappa number 141
  • lignin starts to dissolve rapidly in the relative cooking time of 100, the subsequent step being the main delignification of a successful cooking which is completed by a slow residual delignification towards the end of the cooking.
  • the kappa level of 40 in Test 6 and the kappa level of 15 in Test 7 were achieved. Accordingly, it is obvious that an efficient removal of lignin from prehydrolyzed chip material takes place in the cooking step of the process according to the invention such as disclosed in Test 6; thus, it can replace the sulphate cooking used in Test 7.
  • the tests carried out show that normal technical prehydrolysis conditions inactivate lignin to such an extent that no cooking modification within an acidic or neutral cooking pH range is able to dissolve lignin even though the chip material would be neutralized between the prehydrolysis and the cooking.
  • the sulphite cooking step used in the process according to the invention is operative only when the cooking conditions and the cooking catalyst are chosen appropriately.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • General Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Organic Chemistry (AREA)
  • Paper (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Medicines Containing Material From Animals Or Micro-Organisms (AREA)
  • Amplifiers (AREA)

Claims (4)

  1. Procédé de production d'un hydrolysat d'hémicellulose et d'une pâte spéciale présentant une teneur élevée en alpha-cellulose, comme une pâte dissolvante, à partir d'une matière contenant de la lignocellulose, en deux étapes dont la première comporte une préhydrolyse de ladite matière et la seconde comporte la dissolution de la lignine contenue dans la matière préhydrolysée, à l'aide d'une liqueur de cuisson contenant du sulfite de sodium, de l'hydroxyde de sodium et une anthraquinone, caractérisé en ce que la matière contenant de la lignocellulose est du bois et en ce qu'on effectue la dissolution de la lignine à l'aide d'une liqueur de cuisson contenant de 100 à 400 g de sulfite de sodium par kg de bois sec, de 10 à 100 g de carbonate de sodium par kg de bois sec, assez d'hydroxyde de sodium pour élever le pH de la liqueur de cuisson jusqu'à une valeur initiale située entre 10 et 13, et de 0,01 à 0,2 %, par rapport au bois sec, d'anthraquinone ou d'un de ses dérivés, mais ne contenant pas du tout de sulfure de sodium, à une température de 160°C à 180°C et pendant 100 à 200 minutes, après avoir élevé la température à une vitesse de 0,1 °C à 2°C par minute à partir d'une température située entre la température ambiante et 100°C.
  2. Procédé conforme à la revendication 1, caractérisé en ce que la matière contenant de la lignocellulose est du bois de feuillu.
  3. Procédé conforme à la revendication 1, caractérisé en ce que la matière contenant de la lignocellulose est du bois de résineux.
  4. Procédé conforme à l'une des revendications précédentes, caractérisé en ce que l'on effectue la préhydrolyse à l'aide d'eau, de dioxyde de soufre ou d'acide sulfurique, à une température de 155°C à 170°C et pendant 90 à 170 minutes.
EP88106006A 1987-04-21 1988-04-15 Procédé de fabrication d'un hydrolysat d'hémicellulose et une pâte spéciale Expired - Lifetime EP0287960B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI871730 1987-04-21
FI871730A FI79564C (fi) 1987-04-21 1987-04-21 Foerfarande foer framstaellning av hemicellulosahydrolysat och specialmassa.

Publications (3)

Publication Number Publication Date
EP0287960A2 EP0287960A2 (fr) 1988-10-26
EP0287960A3 EP0287960A3 (fr) 1991-04-17
EP0287960B1 true EP0287960B1 (fr) 1994-09-21

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EP88106006A Expired - Lifetime EP0287960B1 (fr) 1987-04-21 1988-04-15 Procédé de fabrication d'un hydrolysat d'hémicellulose et une pâte spéciale

Country Status (8)

Country Link
EP (1) EP0287960B1 (fr)
AT (1) ATE111986T1 (fr)
BR (1) BR8801894A (fr)
CA (1) CA1295095C (fr)
DE (1) DE3851565T2 (fr)
ES (1) ES2062995T3 (fr)
FI (1) FI79564C (fr)
RU (1) RU1799408C (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12601114B2 (en) 2020-07-06 2026-04-14 Amppc Finland Oy High yield cooking method

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10064131C2 (de) * 2000-12-22 2003-03-27 Sca Hygiene Prod Gmbh Vollgebleichter Sulfit-Zellstoff, Verfahren zu seiner Herstellung und daraus hergestellte Produkte
ATE478096T1 (de) * 2007-11-27 2010-09-15 Innventia Ab Verwendung eines holzhydrolysats

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4213821A (en) * 1976-06-02 1980-07-22 Australian Paper Manufacturers Limited Pulping with quinones and hydroquinones

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3532597A (en) * 1969-03-11 1970-10-06 Uddeholms Ab Preparation of dissolving pulps from wood by hydrolysis and alkaline sulfite digestion
DE2628971A1 (de) * 1976-06-28 1978-01-05 Waldhof Aschaffenburg Papier Verfahren zur herstellung von zellstoff in verbindung mit der gewinnung von holzzuckern
CA1216105A (fr) * 1984-04-06 1987-01-06 C-I-L Inc. Fabrication de la pate a papier

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4213821A (en) * 1976-06-02 1980-07-22 Australian Paper Manufacturers Limited Pulping with quinones and hydroquinones

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12601114B2 (en) 2020-07-06 2026-04-14 Amppc Finland Oy High yield cooking method

Also Published As

Publication number Publication date
FI871730L (fi) 1988-10-22
FI79564C (fi) 1990-01-10
DE3851565T2 (de) 1995-01-26
CA1295095C (fr) 1992-02-04
EP0287960A2 (fr) 1988-10-26
FI871730A0 (fi) 1987-04-21
BR8801894A (pt) 1988-11-22
EP0287960A3 (fr) 1991-04-17
FI79564B (fi) 1989-09-29
DE3851565D1 (de) 1994-10-27
RU1799408C (ru) 1993-02-28
ES2062995T3 (es) 1995-01-01
ATE111986T1 (de) 1994-10-15

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