EP0287960A2 - 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
EP0287960A2
EP0287960A2 EP88106006A EP88106006A EP0287960A2 EP 0287960 A2 EP0287960 A2 EP 0287960A2 EP 88106006 A EP88106006 A EP 88106006A EP 88106006 A EP88106006 A EP 88106006A EP 0287960 A2 EP0287960 A2 EP 0287960A2
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EP
European Patent Office
Prior art keywords
cooking
prehydrolysis
wood
lignin
temperature
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
EP88106006A
Other languages
German (de)
English (en)
Other versions
EP0287960B1 (fr
EP0287960A3 (fr
Inventor
Panu Tikka
Nils Erik Virkola
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.)
SciTech Services Inc
Original Assignee
Suomen Sokeri Oy
SciTech Services Inc
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 Suomen Sokeri Oy, SciTech Services Inc filed Critical Suomen Sokeri Oy
Publication of EP0287960A2 publication Critical patent/EP0287960A2/fr
Publication of EP0287960A3 publication Critical patent/EP0287960A3/fr
Application granted granted Critical
Publication of EP0287960B1 publication Critical patent/EP0287960B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • D21C3/22—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 from a material containing lignocellulose through two steps, the first step comprising the hydrolysis of hemicelluloses into simple sugars and the second step the dissolving of lignin for liberating cellulose fibres.
  • Such additional chemicals used in addition to the basic chemicals of sulphite cooking, include sulphide, white liquor, and anthraquinone, see e.g. Finnish Patent Specification 67 104 and U.S. Patent Specification 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 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.
  • the prehydrolysis-sulphate process has e.g. the following drawbacks: - The yield is low because of the strong alka­line reaction conditions which cause splitting of cel­lulose. Thus the wood consumption per one ton of cel­lulose is high. - The content of residual lignin is rather high because the step for the removal of residual lignin in the sulphate cooking process is extremely non-select­ive.
  • the invention relates to a process for the pro­duction of hemicellulose hydrolysate and special pulp from a material containing lignocellulose through two steps, the first step comprising the prehydrolysis of the material and the second step dissolving of the lignin contained in the prehydrolyzed material.
  • the process is characterized in that the dissolving of lignin is carried out by means of neutral sulphite cooking with anthraquinone or a derivative thereof as a catalyst, the pH of the cooking liquor being in­itially at least 10.
  • 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 preferively consists of softwood or hardwood.
  • the cooking step is suitably carried out with a cooking liquor comprising 100 to 400 g of sodium sul­phite/kg of dry wood; 10 to 100 g of sodium carbon­ate/one kg of dry wood; sodium hydroxide for rising the pH of the cooking liquor to a value between 10 and 13; and 0.01 to 0.2%, calculated on dry wood, of anthraquinone or a derivative thereof.
  • the cooking temperature preferably ranges from 160 to 180°C, and the cooking time is suitably 100 to 200 minutes after the temperature has risen 0.1 to 2°C/min from a temperature varying between room tem­perature and 100°C.
  • 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.
  • the process according to the invention has the following advantages: - The yield of the special pulp to be produced in connection with the production of sugars is in­creased, which improves the production economy. - The process after the prehydrolysis is sim­plified, which decreases the cost of investment. - The easier delignification in the cooking step decreases the need of bleaching, thus improving the production economy and reducing the emission of chlorinated compounds from the bleaching. - The oxygen or peroxide step after the cook­ing is extremely efficient as compared with that of the prehydrolysis-sulphate process, whereby the re­covery and economy are improved. - Small-scale production is economically more interesting because it is possible to operate in con­nection with an existing sodium-based sulphite pulp mill without any appreciable additional investments.
  • 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.
  • 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
  • Wood amount g of abs. dry chips 2500
  • Prehydrolyzing agent SO2 Amount of prehydrolyzing agent, % on dry wood (SO2) 0.25 Liquor ratio 3.5:1
  • Temperature rising time, min 40 Prehydrolysis temperature, °C 155 Prehydrolysis time, min 170
  • Wood amount g of abs. dry chips 2500
  • Prehydrolyzing agent H2SO4 Amount of prehydrolyzing agent, % on dry wood 1.0 Liquor ratio 3.5:1
  • Wood amount g of abs. dry wood 2000 Prehydrolyzing agent H20 Liquor ratio 6:1 Temperature rising time, min 45 Prehydrolysis temperature, °C 170 Prehydrolysis time, min 15 Prehydrolysis loss, % on wood 13.2
  • 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)
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 true EP0287960A2 (fr) 1988-10-26
EP0287960A3 EP0287960A3 (fr) 1991-04-17
EP0287960B1 EP0287960B1 (fr) 1994-09-21

Family

ID=8524351

Family Applications (1)

Application Number Title Priority Date Filing Date
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 (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002052101A1 (fr) * 2000-12-22 2002-07-04 Sca Hygiene Products Gmbh Pate chimique entierement blanchie a base de sulfite, procede de fabrication et produits derives
WO2009068525A1 (fr) * 2007-11-27 2009-06-04 Innventia Ab Utilisation d'un hydrolysat de bois
WO2022008791A1 (fr) 2020-07-06 2022-01-13 Amppc Finland Oy Procédé de cuisson à haut rendement

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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
RYDHOLM, S.E.: "Pulping Processes", 1968, INTERSCIENCE PUBLISHERS, pages: 649 - 672

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002052101A1 (fr) * 2000-12-22 2002-07-04 Sca Hygiene Products Gmbh Pate chimique entierement blanchie a base de sulfite, procede de fabrication et produits derives
DE10064131A1 (de) * 2000-12-22 2002-07-25 Sca Hygiene Prod Gmbh Vollgebleichter Sulfit-Zellstoff, Verfahren zu seiner Herstellung und daraus hergestellte Produkte
DE10064131C2 (de) * 2000-12-22 2003-03-27 Sca Hygiene Prod Gmbh Vollgebleichter Sulfit-Zellstoff, Verfahren zu seiner Herstellung und daraus hergestellte Produkte
WO2009068525A1 (fr) * 2007-11-27 2009-06-04 Innventia Ab Utilisation d'un hydrolysat de bois
EP2067793A1 (fr) * 2007-11-27 2009-06-10 STFI-Packforsk AB Utilisation d'un hydrolysat du bois
WO2022008791A1 (fr) 2020-07-06 2022-01-13 Amppc Finland Oy Procédé de cuisson à haut rendement

Also Published As

Publication number Publication date
EP0287960B1 (fr) 1994-09-21
FI871730L (fi) 1988-10-22
FI79564C (fi) 1990-01-10
DE3851565T2 (de) 1995-01-26
CA1295095C (fr) 1992-02-04
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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