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WO1995018260A1 - Procede de delignification de matieres vegetales ligno-cellulosiques vierges et usees a des fins de production de fibres cellulosiques, de sucres libres et de produits derives de lignine - Google Patents

Procede de delignification de matieres vegetales ligno-cellulosiques vierges et usees a des fins de production de fibres cellulosiques, de sucres libres et de produits derives de lignine Download PDF

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Publication number
WO1995018260A1
WO1995018260A1 PCT/CA1994/000721 CA9400721W WO9518260A1 WO 1995018260 A1 WO1995018260 A1 WO 1995018260A1 CA 9400721 W CA9400721 W CA 9400721W WO 9518260 A1 WO9518260 A1 WO 9518260A1
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WO
WIPO (PCT)
Prior art keywords
lignin
liquid composition
plant
products
composition
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.)
Ceased
Application number
PCT/CA1994/000721
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English (en)
Inventor
Venanzio Di Tullio
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.)
Mauvin Material and Chemical Processing Ltd
Original Assignee
Mauvin Material and Chemical Processing Ltd
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 Mauvin Material and Chemical Processing Ltd filed Critical Mauvin Material and Chemical Processing Ltd
Priority to AU13786/95A priority Critical patent/AU1378695A/en
Publication of WO1995018260A1 publication Critical patent/WO1995018260A1/fr
Anticipated expiration legal-status Critical
Ceased 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
    • D21C3/20—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
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/003—Pulping cellulose-containing materials with organic compounds
    • 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
    • D21C5/02—Working-up waste paper
    • D21C5/022—Chemicals therefor
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/64—Paper recycling

Definitions

  • the Invention relates to a process for the extraction of soluble and solublllzed sugars, lignin and lignin by-products from virgin and non-delignifled post- consumer ligno-celluloslc plant materials.
  • the process is effective in depolymerizing, dissolving, and concentrating the greater part of the lignin and its by-products and some of the sugars.
  • This invention is also directed to the prepara- tion of relatively high brightness pulps which require limited bleaching. DESCRIPTION OF THE PRIOR ART
  • Solvents used are aliphatic and aromatic alcohols, dimethyl sulfoxide, ketones, organic acids and aliphatic esters or a combination of the above in acidic, basic, and neutral solutions (Aziz, S. and McDonough, T.J. TAPPI 70 (3) , 137 (1987) ) .
  • Pulp yields from hardwoods vary In the 50 percentlie range while kappa numbers of 9-30 are common.
  • High temperature solvolysis requires: (1) the use of high pressure equipment which can withstand up to 35 atmospheres of pressure, and
  • the present invention provides a process whereby delignlfication can be realized at much lower temperatures than previously thought possible.
  • a method of delignlfying wood or plant material, both virgin and post-consumer with a recyclable liquid composition comprising:
  • Triethylamine and/or diethylmethylamine and/or dimethyl pyridine and/or methyl pyridine and/or methyl piperldine Up to 10%
  • the invention further provides a method of delignifying a lignin-containing plant-derived material with a recyclable liquid composition comprising water and an organic compound which can be azeotropically purified, said liquid composition having a lower critical solution temperature of between 0°C and 100°C above which lower critical solution temperature said liquid composition divides into a heavier aqueous phase and a lighter organic phase, which method comprises: treating said lignin-containing plant derived material with a lignin-removing amount of said liquid composition at a temperature between 100 °C and 210 °C for sufficient time to release lignin from said lignin-contain ⁇ ing plant-derived material.
  • the operating temperature range is usually 100-
  • Amounts of neutralizing agents such as sodium hydroxide, potassium hydroxide or sodium silicate, if present, usually comprise up to about 2.5% by weight. If used, preferably at least about 0.003% by weight of such a neutralizing agent is employed. A particular select range is 0.25-1.0% by weight.
  • the method usually requires at least 20 minutes, preferably 20-30 minutes, especially 20-60 minutes.
  • the method can be employed upon virgin lignin- containing plant material such as wood or it can be employ- ed on recycled post-consumer fiber products which have not been delignlfled such as TMP newsprint.
  • the organosolv (a solvent system with a lower critical solution temperature or LCST, i.e. as the temperature is raised the mutual solubilities of the two solvent constituents decrease until above a certain criti ⁇ cal temperature a blphasic mixture is formed) is used to separate mono and disaccharides from the remainder of the polysaccharide/lignin complex (A.I. Vogel, Practical
  • the organosolv at basic pH, is used to depolymerize the saccharide-lignin complex, and further (3) the organosolv is used to dissolve low molecular weight saccharldes while depolymerizing lignin thus freeing the alpha cellulose fraction for recovery.
  • alkoxy ethanol ethers form crown ether complexes with alkali cations, thus generating anions of enhanced chemical activity which may account for the ease of depolymerlzation (Glymes: The Grant Family of Glycol Ethers-Ferro Corporation Publication; Stephenson, R.J. Chem. Eng. Data 1993 38 134) .
  • the present invention thus provides a mechanism by which the reaction rate of delignlfication and desac- charification of ligno-celluloslc complexes can be enhanced.
  • Lower critical solution temperature solvents have the further distinction of separating into blphasic mix ⁇ tures of disproportionate lipophilicity by raising their temperature or inorganic salt solution content to, for example, 1-2% by weight (Glycol Ethers Technical Brochure F-60617 10/89-5M (Union Carbide Chemicals and Plastics Company Inc.)).
  • Organosolvs which have lower critical solution temperatures have the further capability of proportioning, with bias, lipophilic material to the upper phase, and hydrophllic material to the lower phase.
  • the ability to simultaneously raise the lipo ⁇ philic and hydrophllic properties of the solution by causing a biphase to form greatly enhances both the cata ⁇ lytic capabilities of the solution and solubility of the respective layers to lignin degradation by-products and soluble saccharides.
  • the present invention provides a method of solu- bilizing mono and disaccharides with a recyclable liquid composition (Composition A) comprising:
  • composition B a recyclable liquid composition comprising:
  • Triethyl amine and/or diethyl methyl amine and/or methyl pyridine and/or dimethyl pyridine and/or methyl piperidine 0-10% Water up to 100%
  • the present invention further provides a method of sequentially extracting low molecular weight sugars, solublllzed low molecular weight sugars, lignin and depoly- erlzed lignin with a recyclable liquid composition from the ligno-cellulosic plant materials.
  • a system which: 1) has the versatility to process a broad spectrum of ligno-celluloslc species.
  • FIGURE 1 is a schematic of events in a particular embodiment directed to explaining isolation of the products .
  • a mixture of lipophllic compound which exhibits a lower critical solution temperature in water is used for extraction of free mono- and disaccharides.
  • Another embodiment of the invention relates to the use of solutions which have a lower critical solution temperature i.e. three levels of lipophilicity can be incorporated into one solution by changing the temperature and/or salt concentration and/or solvent concentrations.
  • the single phase composition employed must be capable of generating an aqueous and an organic phase above the lower critical solution temperature i.e. showing decreasing mutual solubility with an increase in tempera- ture (e.g. as shown with water-glycol ethers by Stephenson R.M.; J.Chem.Eng.Data 1993, 38, 134-138).
  • the composition comprises one phase; above it it comprises two p h ases.
  • the cr ⁇ tical temperature is between 0 °C and about 100 °C preferably below 50 °C.
  • the composition is used for delignlfication of ligno-cellulosic materials, depolymerlzation of the freed lignin, and hydrolysis of the lower molecular weight sugars.
  • the composition is further used above the lower critical solution temperature to separate the blphasic layers, one rich in lipophillc and the other rich ln hydro ⁇ phllic components.
  • compositions of the invention include Compositions A and B as described above.
  • composition A is the same as composition B but does not contain sodium silicate and hydroxide. It is a subset of composition B which is neutral ln pH and free of salts.
  • a specific composition of interest is:
  • composition B Addition of 5% by weight of Inorganic alkali agents such as sodium hydroxide and sodium silicate to the solution i.e. formation of composition B, causes the ligno- celluloslc bonds to rupture and the free lignin to depoly- erize. Depolymerized lignin oils can be recovered.
  • Inorganic alkali agents such as sodium hydroxide and sodium silicate
  • mixed groundwood fiber it is desir ⁇ able to carry out the extraction at elevated temperatures of 100-210 °C, but preferably at 127 °C for 1 to 2 hours.
  • the method of the invention allows for isolation of lignin and/or depolymerized lignin by-products, without substantial condensation of lignin on cellulose fiber.
  • the biphasic solvent mixture was split into the upper and lower layers. Lignin and lignin by-products and sugars are collected in the upper and lower phases (layers) respectively. After extraction of lignin a low-lignin cellulose can be obtained. The darker upper layer was neutralized with concentrated hydrochloric acid and concentrated at reduced pressure. Distillation of the mother liquor at 1 mm pressure gave three oil fractions and a solid lignin residue.
  • chromophoric groups ln isolated pulp or extracted oil can be oxidized with an oxidizing agent .
  • sodium hydroxide and sodium silicate can neutralize acids, and make organic salts which are calcium based more soluble by exchanging the calcium ion for sodium.
  • sodium silicate increases the wetting power of the solution.
  • Potassium hydroxide can be expected to work as an alternate to sodium hydroxide.
  • the fibrous Insoluble residue separated from the liquid was cellulose. Not all lignin had been removed since kappa numbers of 20-30 were obtained. The yield of cellulose was above 60%.
  • a solvent which has a lower critical solution temperature (LCST) (against water) of 0 to 100 °C, prefer- ably between 12 and 50 °C, and having the ability to dis ⁇ solve organic compounds is an essential constituent of the mixture.
  • LCST critical solution temperature
  • Some examples of such solvents are found in the table below. The numbers in brackets are the lower criti ⁇ cal solution temperatures. A range is given when a mixture of isomers is involved.
  • Dimethyl pyridine (-3 to 34 °C), 3-methyl pyri ⁇ dine (49 °C), butoxy ethanol (49 °C), isobutoxy ethanol (24 °C), hexamethyleneimine (67 °C), methyl diethyla ine (49 °C), triethylamine (12-18 °C), 2 and 3 methyl piperl- dine (79 and 57 °C), 1,2 propylene glycol-1-propylether (34 °C) and 1,2 propylene glycol -2-propylether (43 °C) .
  • A.W. Francis, Critical Solution Temperatures, Advances in Chemistry Series #31 1961:American Chemical Society. - (Note:Dimethyl pyridine is made of three isomers. Depend- ing on the mixture used the LCST can range from -3 to
  • LCST solvent For purposes of simplicity and example we used butoxy ethanol as the LCST solvent.
  • the reason for using a LCST solvent is in order to take advantage of its capability to selectively change the solubilities of the solution by either increasing salt concentration or temperature.
  • a further reason is to partition the extracted materials between the two layers formed thus using this phenomenon for partial isolation of the extractants and for purification of the solvent.
  • Salt concen ration and/or temperature can be used to temporarily generate a two phase system in order to solubilize specific organic compounds. Upon isolation of the extraction, the two phase system can be reverted to one phase at will.
  • the fibrous plant material is preferably prepared e.g. by chipping, shredding or forming shavings.
  • the prepared plant material is then treated (step 2.0) with composition A (which lacks neutralizing agents). Soluble sugar and lignin can then be removed (step 2.1). Further extraction using composition B (step 3.0) leads to lignin and lignin by-products and sugar which can be Isolated from the fiber and from each other using the mutual insolubility of the LCST liquid composition compo ⁇ nents (step 3.1) above the LCST.
  • step 3.0.1 Further extraction using composition B ln the presence of a bleaching agent such as hydrogen peroxide (step 3.0.1) leads to bleached lignin and bleached lignin by-products and sugar which can be isolated from the fiber and from each other using the mutual Insolubility of the LCST liquid composition components (step 3.0.2) above the LCST. Insoluble cellulose fiber is then collected (step 4.0) .
  • a bleaching agent such as hydrogen peroxide
  • a single extraction or multiple extractions can be made depending upon the starting materials and end- products desired.
  • the optional bleaching step can be integrated as shown or can be carried out separately.
  • a further advantage of the invention is that bleaching by hydrogen peroxide (preferably 3-35% strength) is possible by introducing the bleaching agent into the solution with no known detrimental effects to its efficacy.
  • Hypochlorite e.g. 1-5% strength
  • Elemental oxygen usually at low pressure is a further alternative bleaching agent.
  • the following example was carried out by solvent extracting lOOg of microwave dried maple : birch : poplar shavings (50:35:15) with 1.75 liters of the variant of composition B.
  • the mixture was heated to 127 °C for 1 hour. A fresh charge was added and the wood fiber reheated for another hour.
  • the wood fiber was then refined in an osterizer for 2 minutes (liquify).
  • the pulp was next washed with 2 charges of water. At each charge the pulp fiber was further refined in the osterizer for 2 minutes.
  • the consistency was then raised to 50%, i.e. by means of ricer, and dried in a microwave oven (low).
  • the fiber was dried at 110 °C for 4 hours before being weighed. A yield of 64.2% was obtained.
  • the slightly yellow unbleached fiber had a kappa number of 24 and an ISO brightness of 67.
  • the upper layer of the LCST solution was neutralized with concentrated hydrochloric acid, and reduced in volume on a rotatory evaporator under vacuum. Salt which precipitated was separated from the oil layer. Distillation at 1.5 mm pressure of the remaining "88 ml of oil gave the following fractions: FRACTION b.P. RANGE mis. COMMENT

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Toxicology (AREA)
  • Paper (AREA)
  • Compounds Of Unknown Constitution (AREA)

Abstract

Procédé de production de sucres libres, de lignine, de produits dérivés de lignine et de pâte cellulosique au moyen de solvants recyclables présentant des températures de solution critiques inférieures.
PCT/CA1994/000721 1993-12-28 1994-12-28 Procede de delignification de matieres vegetales ligno-cellulosiques vierges et usees a des fins de production de fibres cellulosiques, de sucres libres et de produits derives de lignine Ceased WO1995018260A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU13786/95A AU1378695A (en) 1993-12-28 1994-12-28 Process for delignifying virgin and post-consumer used ligno-cellulosic plant meterials for the purpose of preparing cellulosic fiber, free sugars and lignin by-products

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US17407193A 1993-12-28 1993-12-28
US174,071 1993-12-28

Publications (1)

Publication Number Publication Date
WO1995018260A1 true WO1995018260A1 (fr) 1995-07-06

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PCT/CA1994/000721 Ceased WO1995018260A1 (fr) 1993-12-28 1994-12-28 Procede de delignification de matieres vegetales ligno-cellulosiques vierges et usees a des fins de production de fibres cellulosiques, de sucres libres et de produits derives de lignine

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AU (1) AU1378695A (fr)
WO (1) WO1995018260A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2489780A1 (fr) 2011-02-16 2012-08-22 Rheinisch-Westfälisch-Technische Hochschule Aachen Procédé intégré pour le fractionnement sélectif et la séparation de la lignocellulose en ses principaux composants

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4248663A (en) * 1978-07-05 1981-02-03 Pulp And Paper Research Institute Of Canada Pulping with an alkaline liquor containing a cyclic keto compound and an amino compound
DE3207157C1 (de) * 1982-02-27 1983-06-09 Degussa Ag, 6000 Frankfurt Verfahren zur Herstellung von halbgebleichten Zellstoffen
EP0335260A2 (fr) * 1988-03-31 1989-10-04 Chemische Fabrik Grünau GmbH Procédé de désencrage de vieux papier imprimé par flottation
WO1994001614A2 (fr) * 1992-07-08 1994-01-20 Mauvin Material And Chemical Processing Limited Procede de desencrage du papier et de nettoyage des feutres

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4248663A (en) * 1978-07-05 1981-02-03 Pulp And Paper Research Institute Of Canada Pulping with an alkaline liquor containing a cyclic keto compound and an amino compound
DE3207157C1 (de) * 1982-02-27 1983-06-09 Degussa Ag, 6000 Frankfurt Verfahren zur Herstellung von halbgebleichten Zellstoffen
EP0335260A2 (fr) * 1988-03-31 1989-10-04 Chemische Fabrik Grünau GmbH Procédé de désencrage de vieux papier imprimé par flottation
WO1994001614A2 (fr) * 1992-07-08 1994-01-20 Mauvin Material And Chemical Processing Limited Procede de desencrage du papier et de nettoyage des feutres

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2489780A1 (fr) 2011-02-16 2012-08-22 Rheinisch-Westfälisch-Technische Hochschule Aachen Procédé intégré pour le fractionnement sélectif et la séparation de la lignocellulose en ses principaux composants
WO2012110231A1 (fr) 2011-02-16 2012-08-23 Rheinisch-Westfälische Technische Hochschule Processus intégré de fractionnement sélectif et de séparation de la lignocellulose en ses composants principaux

Also Published As

Publication number Publication date
AU1378695A (en) 1995-07-17

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