WO2001030855A1 - Procede de production de pate cellulosique - Google Patents

Procede de production de pate cellulosique Download PDF

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Publication number
WO2001030855A1
WO2001030855A1 PCT/PL2000/000071 PL0000071W WO0130855A1 WO 2001030855 A1 WO2001030855 A1 WO 2001030855A1 PL 0000071 W PL0000071 W PL 0000071W WO 0130855 A1 WO0130855 A1 WO 0130855A1
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WO
WIPO (PCT)
Prior art keywords
cellulose pulp
cellulose
water
pulp
hydrothermal treatment
Prior art date
Application number
PCT/PL2000/000071
Other languages
English (en)
Inventor
Henryk Struszczyk
Dariusz Wawro
Alojzy Urbanowski
Włodzimierz MIKOŁAJCZYK
Paweł STAROSTKA
Wacław TOMASZEWSKI
Danuta CIECHAŃSKA
Original Assignee
Instytut Włokien Chemicznych
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 Instytut Włokien Chemicznych filed Critical Instytut Włokien Chemicznych
Publication of WO2001030855A1 publication Critical patent/WO2001030855A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
    • C08B1/003—Preparation of cellulose solutions, i.e. dopes, with different possible solvents, e.g. ionic liquids

Definitions

  • the object of the invention is a method to produce modified cellulose pulp with improved reactivity and solubility in aqueous solutions of amine oxides.
  • the well-known methods to modify cellulose pulp do not assure a sufficient improvement of the pulp's reactivity for the production of cellulose derivatives like esters and ethers and for improving the quality of solutions of cellulose derivatives including the filterability of cellulos xantate alkaline solutions.
  • the well-known methods do not allow to sufficiently fast dissolve the cellulose pulp in aqueous amine oxides to avoid the quality - deteriorating degradation of cellulose.
  • the present invention consists in the hydrothermal treatment of cellulose pulp with hot water and/or water steam at temperature in the range 100 - 200°C and pressure 0.1 - 1.0 MPa and at a water pulp weight proportion of 5: 1 during a time of at least 1 minute.
  • activators organic and / or inorganic acids like acetic-, formic-, citric-, ascorbic-, succinic-, hydrochloric-, sulfuric acid and / or their salts like ammonium persulfate, ammonium chloride and / or amines and their derivatives like diethyleneamine, triethyleneamine, hydroxylamine sulfate, imidazol, hydrazine sulfate, guanidine sulfate, urea in a weight proportion to cellulose not less than 0.01 preferably 0.1 to 0.5 weight parts.
  • the obtained modified cellulose pulp is possibly purified with water and dried at 105°C.
  • the activator are introduced before and/or during the defibration process and/or during the hydrothermal treatment.
  • the aqueous medium is preferably circulated and the reaction mass is agitated.
  • the modified cellulose pulp obtained according to the invention, is characterized by a controlled polymerization degree not lower than 200, a water retention value (WRV) higher by at least 10% than for the initial cellulose pulp, value of hydrogen bonds in the range 15 - 20 kJ/mol, reactivity higher by at least 50% than for the initial pulp and a multifold increased solubility in aqueous solutions of amine oxides.
  • WRV water retention value
  • the hydrothermal treatment of the initial cellulose pulp improves its reactivity because the inner structure of cellulose is during the process made better accessible for the modifying substances leading to forming of esters and ethers of cellulose.
  • the average polymerization degree and polydispersity is lowered in a controlled way by several to several tens percents depending upon the applied activator and the hydrogen bonds are weakened both the interbonds between the cellulose molecule chains as the intrabonds within the cellulose molecules.
  • the hydrothermally modified cellulose pulp with controlled molecular, supermolecular and mo ⁇ hological structure presents a profoundly better reactivity in a number of processes applied for the production of cellulose derivatives i.e.
  • the other merit of the invention is that the hydrothermally treated cellulose is obtained with an insignificant loss of the pulp mass not exceeding 1% wt which results from saccharification of cellulose.
  • the initial defibration of the cellulose pulp makes it swell which may be accompanied by the intercalation of the activator into the structure of the polymer easing the following hydrothermal treatment.
  • One other advantage of the invention is the possibility of using a dried or never - dried pulp for the hydrothermal treatment.
  • the activators used in the invention depending - upon their nature i.e. Lewis acides or alkalies cause defined changes in the molecular structure of cellulose essentially influencing its supermolecular and mo ⁇ hological structure.
  • the advantage of the used activators is the controlled change of the structure of cellulose allowing to attain the assumed reactivity in the process of manufacturing cellulose derivatives and the improved solubility in aqueous amine oxide solutions.
  • the modified cellulose pulp, made according to the invention is suitable for the manufacture of cellulose derivatives for the textile-, food-, chemical-, plastics- and dyestuff industries and for obtaining aqueous solutions of cellulose in amine oxides in the manufacture of fibres film and other cellulosic products.
  • Viscose was prepared according the test X - based on the reactivity of alkalicellulose toward 28, 34, 40 and 46 wt% of carbon disulfide.
  • - Reactivity of the pulp in the acetylation process was determined by -the estimation of acetic groups in the product obtained in the reaction of lg of cellulose pulp with 20 cm acetic anhydride at 25°C during 3 minutes. Prior to that the cellulose pulp was dispergated during 10 minutes at 25°C in a mixture of 10 cm of acetic acid and 10 cm hexane with 0.01 g of perchloric acid. The obtained cellulose acetate was washed with water to a complete removal of the acetic acid and dried. - Reactivity of cellulose in the carboxy methylation process - was evaluated by estimation of the content of carboxymety 1 groups.
  • the obtained dispersion was left at this temperature for 12 hours at 20°C and then put into an autoclave with agitator and subjected to hydrothermal treatment at 163°C under a pressure of 0.58 MPa for 165 minutes. Then the cellulose dispersion was filtered, washed with water to complete removal of the by-products and dried to constant weight.
  • the modified cellulose pulp completely dissolved after 10 minutes in an aqueous solution of N-methylmorpholine oxide, while the initial pulp dissolved barely after 60 minutes under the same conditions.
  • the obtained suspension was introduced to an autoclave with agitator and was subjected to hydrothermal treatment at 162°C under a pressure of 0.55 MPa for 210 minutes, there the obtained cellulose pulp was purified and dried as in Example 1.
  • the estimation of the pulp's reactivity toward acetic anhydride gave the result of substitution degree 20.6% meaning a 74%o increase compared to the initial cellulose pulp.
  • the modified cellulose pulp completely dissolved after 10 minutes in an aqueous solution of N- methylmo ⁇ holine oxide while the initial cellulose pulp under the same conditions was dissolved after 60 minutes.
  • the suspension was maintained at 20°C for 16 hours and next introduced to an autoclave with agitator and subjected for 90 minutes to hydrothermal treatment at 162°C and pressure of 0.54 MPa in the presence of 0.5 part by weight of ascorbic acid as activator.
  • the obtained product was purified and dried as in Example 1.
  • the percentage of substituted groups determined as reactivity to acetic anhydride was 23.1% meaning an increase by 69% compared to reactivity of the initial cellulose pulp.
  • the modified cellulose pulp dissolved within 20 minutes in an aqueous solution of N-methylmo ⁇ holine oxide while the initial cellulose pulp was dissolved only after 80 minutes.
  • Example 7 400 parts by weight of cellulose pulp having properties as in Example 7 were defibrated as in Example 7. To the prepared suspension 1 part by weight of guanidine carbonate was added. The suspension was subjected to hydrothermal treatment at 162°C and pressure of 0.57 MPa for 180 minutes. The obtained product was purified and dried as in Example 1.
  • the modified cellulose pulp completely dissolved in an aqueous solution of N- methylmo ⁇ holine oxide within 30 minutes compared to 120 minutes for the initial cellulose pulp under the same conditiones.
  • the percentage of substituted acetate groups after the estimation of the pulp's reactivity to acetate anhydride was 17.5%, an increase by 139% compared to the reactivity of the initial cellulose pulp, whose substituted groups percentage was 7.3%.
  • the modified cellulose pulp completely dissolved in an aqueous solution of N- methylmo ⁇ holine oxide within 20 minutes compared to 60 minutes for the initial cellulose pulp under the same conditions.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Paper (AREA)

Abstract

La présente invention concerne un procédé destiné à produire une pâte cellulosique modifiée possédant une réactivité et une solubilité améliorées dans des solutions aqueuses d'oxydes d'amines. Dans ce procédé, la cellulose de départ subit un processus hydrothermique avec de l'eau et/ou de la vapeur à une température comprise entre 100 et 200 °C et sous une pression comprise entre 0,1 et 1,0 MPa, avec un rapport eau/cellulose d'au moins 5:1 en poids, pendant une durée d'au moins une minute, et de préférence en présence d'activateurs. La pâte à papier cellulosique obtenue est éventuellement lavée à l'eau et séchée à une température inférieure à 105 °C.
PCT/PL2000/000071 1999-10-29 2000-10-13 Procede de production de pate cellulosique WO2001030855A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
PL33636399A PL336363A1 (en) 1999-10-29 1999-10-29 Method of obtaining a modified cellulose pulp
PLP.336363 1999-10-29

Publications (1)

Publication Number Publication Date
WO2001030855A1 true WO2001030855A1 (fr) 2001-05-03

Family

ID=20075378

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/PL2000/000071 WO2001030855A1 (fr) 1999-10-29 2000-10-13 Procede de production de pate cellulosique

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PL (1) PL336363A1 (fr)
WO (1) WO2001030855A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002022924A1 (fr) * 2000-09-13 2002-03-21 Instytut Wlókien Chemicznych Procede de production de fibres, de films, de boitiers et d'autres produits a partir de cellulose soluble modifiee
CN106283242A (zh) * 2015-06-01 2017-01-04 中国纺织科学研究院 一种纤维素浆粕的活化方法
US10612059B2 (en) 2015-04-10 2020-04-07 Comet Biorefining Inc. Methods and compositions for the treatment of cellulosic biomass and products produced thereby
US10633461B2 (en) 2018-05-10 2020-04-28 Comet Biorefining Inc. Compositions comprising glucose and hemicellulose and their use
CN117626701A (zh) * 2023-11-21 2024-03-01 恩平三力胶粘制品有限公司 一种非极性绵纸及其制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD298789B5 (de) * 1990-05-10 1994-07-21 Thueringisches Inst Textil Verfahren zur Aktivierung cellulosischer Faserrohstoffe
DE4439149A1 (de) * 1994-11-03 1996-05-09 Thueringisches Inst Textil Verfahren zur Herstellung einer homogenen Celluloselösung
US5831076A (en) * 1996-08-31 1998-11-03 Zimmer Aktiengesellschaft Production of cellulose carbamate with improved solubility properties
US5906926A (en) * 1997-04-15 1999-05-25 Zimmer Aktiengesellschaft Method for modified manufacture of cellulose carbamate
EP0918101A1 (fr) * 1997-11-20 1999-05-26 Instytut Wlokien Chemicznych Procédé pour la fabrication d'objets cellulosiques
DE19817454A1 (de) * 1998-04-20 1999-10-21 Wolff Walsrode Ag Verfahren zur Aktivierung und Derivatisierung von Cellulose

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD298789B5 (de) * 1990-05-10 1994-07-21 Thueringisches Inst Textil Verfahren zur Aktivierung cellulosischer Faserrohstoffe
DE4439149A1 (de) * 1994-11-03 1996-05-09 Thueringisches Inst Textil Verfahren zur Herstellung einer homogenen Celluloselösung
US5831076A (en) * 1996-08-31 1998-11-03 Zimmer Aktiengesellschaft Production of cellulose carbamate with improved solubility properties
US5906926A (en) * 1997-04-15 1999-05-25 Zimmer Aktiengesellschaft Method for modified manufacture of cellulose carbamate
EP0918101A1 (fr) * 1997-11-20 1999-05-26 Instytut Wlokien Chemicznych Procédé pour la fabrication d'objets cellulosiques
DE19817454A1 (de) * 1998-04-20 1999-10-21 Wolff Walsrode Ag Verfahren zur Aktivierung und Derivatisierung von Cellulose

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MICHELS C ET AL: "CHARACTERISTICS OF THE AMINE OXIDE PROCESS DEVELOPED AT THE TURING INSTITUTE OF TEXTILES AND PLASTICS", FIBRE CHEMISTRY,US,CONSULTANTS BUREAU. NEW YORK, vol. 28, no. 1, 1996, pages 17 - 21, XP000633424, ISSN: 0015-0541 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002022924A1 (fr) * 2000-09-13 2002-03-21 Instytut Wlókien Chemicznych Procede de production de fibres, de films, de boitiers et d'autres produits a partir de cellulose soluble modifiee
US10612059B2 (en) 2015-04-10 2020-04-07 Comet Biorefining Inc. Methods and compositions for the treatment of cellulosic biomass and products produced thereby
US11692211B2 (en) 2015-04-10 2023-07-04 Comet Biorefining Inc. Methods and compositions for the treatment of cellulosic biomass and products produced thereby
CN106283242A (zh) * 2015-06-01 2017-01-04 中国纺织科学研究院 一种纤维素浆粕的活化方法
CN106283242B (zh) * 2015-06-01 2019-01-08 中国纺织科学研究院 一种纤维素浆粕的活化方法
US10633461B2 (en) 2018-05-10 2020-04-28 Comet Biorefining Inc. Compositions comprising glucose and hemicellulose and their use
US11525016B2 (en) 2018-05-10 2022-12-13 Comet Biorefining Inc. Compositions comprising glucose and hemicellulose and their use
CN117626701A (zh) * 2023-11-21 2024-03-01 恩平三力胶粘制品有限公司 一种非极性绵纸及其制备方法

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Publication number Publication date
PL336363A1 (en) 2001-05-07

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