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WO2012022325A2 - Procédé pour dissoudre de la cellulose - Google Patents

Procédé pour dissoudre de la cellulose Download PDF

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Publication number
WO2012022325A2
WO2012022325A2 PCT/DE2011/075145 DE2011075145W WO2012022325A2 WO 2012022325 A2 WO2012022325 A2 WO 2012022325A2 DE 2011075145 W DE2011075145 W DE 2011075145W WO 2012022325 A2 WO2012022325 A2 WO 2012022325A2
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WO
WIPO (PCT)
Prior art keywords
cellulose
alkyl
organic
added
stirring
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/DE2011/075145
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German (de)
English (en)
Other versions
WO2012022325A3 (fr
Inventor
Roberto Rinaldi
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.)
Studiengesellschaft Kohle gGmbH
Original Assignee
Studiengesellschaft Kohle gGmbH
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 Studiengesellschaft Kohle gGmbH filed Critical Studiengesellschaft Kohle gGmbH
Publication of WO2012022325A2 publication Critical patent/WO2012022325A2/fr
Publication of WO2012022325A3 publication Critical patent/WO2012022325A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B16/00—Regeneration of cellulose

Definitions

  • the present invention relates to a process for dissolving cellulose.
  • Cellulose is the main constituent of plant cell walls and is the world's most abundant organic polymer compound, accounting for approximately 1,200 billion tonnes. It is therefore the most common polysaccharide.
  • Chemically, the cellulose is an unbranched polysaccharide consisting of several hundred to ten thousand ß-D-glucose molecules. The number of ⁇ -D-glucose units is defined as the degree of polymerization of the cellulose (P w - weight average of the degree of polymerization, P n - number average of the degree of polymerization). It is an important technical raw material used as a raw material in the paper industry or in the clothing industry as viscose, cotton fiber or linen.
  • cellulose derivatives such as methyl cellulose are used as flow improvers, etc.
  • Further fields of application are the production of cellophane or the development of regenerative car fuels, such as cellulose ethanol, which is produced from vegetable biomass.
  • cellulose derivatives are used as additives in the food and pharmaceutical industries. For this purpose, it is necessary to digest the biomass to an extent, ie to separate into their individual components, so that they can then be processed into corresponding products. Without chemical disruption, z. As cellulose hydrolysis, the cellulose is hardly suitable for enzymatic processes.
  • Cellulose is insoluble in water and in most organic solvents. It has some solubility in toxic solvents such as CS 2, amines, morpholines, etc., concentrated mineral acids, molten salts, and copper ammonia.
  • toxic solvents such as CS 2, amines, morpholines, etc., concentrated mineral acids, molten salts, and copper ammonia.
  • solvents are, for example, N-methylmorpholine-N-oxide and CS 2 .
  • a process for the dissolution of cellulose in which cellulose-containing material is heated in a mixture of a dipolar aprotic intergranular swelling agent and an ionic liquid for a certain time at a temperature between 25 ° C and 180 ° C.
  • the molar ratio of dipolar aprotic intergranular swelling agent and the ionic liquid is 0.5 to 25 mol of the dipolar aprotic intergranular swelling agent based on 1 mol of the ionic liquid.
  • Object of the present invention is accordingly to provide a method for dissolving cellulose, in which the cellulose can be brought into solution immediately and with as much waiver of toxic solvents in solution and fed in dissolved form in a conventional manner for further processing can.
  • a cellulose-containing material is suspended in a polar aprotic solvent and one or more organic or inorganic salts are added to the resulting suspension.
  • the process step of first suspending the cellulose-containing material in the polar aprotic solvent and then adding one or more organic or inorganic salts the cellulose-containing material is almost spontaneously, i. immediately after addition of the salt or salts, dissolves.
  • the dissolution process is preferably carried out in a temperature range of 0 ° C to 200 ° C, preferably from 20 ° C to 1 10 ° C.
  • the dissolution process can be accelerated if the resulting mixture is heated to a temperature above 50 ° C, in particular between 80 ° C and 150 ° C.
  • any cellulose-based materials can be used, such as. Microcrystalline cellulose, cr-cellulose, mechanically treated cellulose or wood pulp.
  • the origin may be arbitrary, the cellulosic material may consist of wood, oilseeds, beans, cereals and cereal fibers, cotton, sugarcane, all parts can be used, i. Leaves, stems, stems, shells, pods, flower parts etc.
  • polar aprotic solvents are not limited to specific solvents.
  • the dissolution process of the cellulose is particularly fast when the polar aprotic solvent is selected from compounds of general formula I. O
  • R and R 2 may be identical or different and are H, C 1 -C 6 -alkyl or C (O) R 3 , where R 3 may be H or C 1 -C 6 -alkyl, and
  • A is H, C 1 -C 6 -alkyl or NR 4 R 5 , where R 4 and R 5 may be identical or different and are H or C 1 -C 6 -alkyl and
  • a and R or R 2 may be connected to each other by ring formation.
  • solvents examples include 2-pyrrolidinone, ⁇ -valerolactam, ⁇ -caprolactam, 1-methyl-2-pyrrolidinone (NMP), 1, 3-dimethyl-2-imidazolidinone (DMI), 1, 1, 3,3- Tetramethylurea, ⁇ , ⁇ -dimethylacetamide (DMA), ⁇ , ⁇ -dimethylformamide (DMF), acetylamine and any mixtures of the foregoing.
  • NMP 2-pyrrolidinone
  • DMI 1, 3-dimethyl-2-imidazolidinone
  • DMA ⁇ -dimethylacetamide
  • DMF ⁇ , ⁇ -dimethylformamide
  • acetylamine any mixtures of the foregoing.
  • Ionic liquids are liquid salts that are liquid at temperatures below 100 ° C.
  • Examples of cations used are alkylated imidazolium, pyridinium, ammonium or phosphonium ions.
  • As anions a wide variety of ions can be used, ranging from simple halides over more complex inorganic ions such as tetrafluoroborates to large organic ions such as trifluororomethanesulfonamide. Examples of suitable ionic liquids are described in the patents US-A1 943, 176, WO 03/029329, WO 07/057235.
  • suitable ionic liquids are preferably as cations Dialkylimidazolium, alkylpyridinium, tetraalkylammonium, tetraalkylphosphonium.
  • the anions are preferably selected from chloride, bromide, nitrate, sulfate, phosphate, dicyanamide, tetrafluoroborate, tetrachloroaluminate, tetrachloroferrate (III), hexafluorophosphate, hexafluoroantimonate, carboxylic anions, trifluoromethanesulfonate, C 1 -C 4 -alkyl phosphate, C 4 -alkyl sulfate, C 1 -C 4 4- alkyl sulfonate, benzenesulfonate,
  • the cations and anions can be combined as desired.
  • Particularly suitable ionic liquids have proven to be alkylated imidazolium, pyridinium, ammonium or phosphonium radicals and as anions halides, inorganic, complex anions, such as tetrafluoroborates, or organic ions such as trifluoromethanesulfonamides.
  • cellulose dissolves immediately in a mixture of an aprotic polar solvent and a salt, preferably an ionic liquid, when first preparing a suspension of the cellulose-containing material in the solvent and then the salt, in solid or liquid Form, is added. Within a short time, often immediately, a clear cellulose solution is obtained.
  • the polar aprotic solvent and the salt are preferably present in a molar ratio of 0.8: 1 to 15: 1.
  • the dissolved cellulose can be recovered in a conventional manner from the solution.
  • the solution is treated with a polar solvent such as water, ammonia (in liquid form), dichloromethane, methanol, ethanol, isopropanol and other alcohols.
  • a polar solvent such as water, ammonia (in liquid form), dichloromethane, methanol, ethanol, isopropanol and other alcohols.
  • the precipitated cellulose can be isolated in a manner known per se, for example by simple filtration.
  • the filtrate, the mixture of aprotic solvent, salt and precipitation solvent can be worked up in a conventional manner or fed as such for further use.
  • the concentration of cellulose in the solution can be up to 30 wt .-%.
  • the separated cellulose or the resulting solution can be further processed in a conventional manner.
  • Cellulosic materials include any of the cellulosic materials available on the market or found in nature, including pure cellulose, crop residues, straw, wood, and paper.
  • microcrystalline cellulose (Avicel ®, Aldrich) were dissolved in 40 ml of an organic electrolyte solution containing 50 wt .-% 1-butyl-3-methylimidazolium chloride in 1, 3-dimethyl-2- imidazolidinone contains. The mixture was heated to 100 ° C and stirred. After stirring for 15 minutes, the cellulose was dissolved.
  • microcrystalline cellulose (Avicel ®, Aldrich) were added with stirring at 100 ° C to 20 ml of 1, 3-dimethyl-2-imidazolidinone. Subsequently, 12 g of 1-ethyl-3-methylimidazolium acetate were added to the cellulosic suspension. It spontaneously formed a clear cellulose solution with stirring at 100 ° C.
  • microcrystalline cellulose (Avicel ®, Aldrich) were added with stirring at 100 ° C to 20 ml of 1, 3-dimethyl-2-imidazolidinone. Subsequently, 22 g of 1-ethyl-3-methylimidazolium acetate were added to the cellulosic suspension. Within less than a minute, with stirring at 100 ° C, a clear cellulose solution was obtained.
  • ⁇ -cellulose (Aldrich) were added with stirring at 100 ° C to 20 ml of 1, 3-dimethyl-2-imidazolidinone. Subsequently, 20 g of 1-butyl-3-methylimidazolium chloride was added to the cellulose solution. After five minutes stirring at 100 ° C, a clear cellulose solution was obtained.
  • ⁇ -cellulose (2 g, Aldrich) was added with stirring at 100 ° C in 20 ml of 1, 3-dimethyl-2-imidazolidinone. Subsequently, 20 g of 1-butyl-3-methylimidazolium chloride was added to the cellulosic suspension. Immediately a clear solution was obtained at 100 ° C.
  • microcrystalline cellulose (Avicel ®, Aldrich) was added in 5 ml 2-pyrolidinone with stirring at 100 ° C. Subsequently, 5 ml of 1-ethyl-3-methylimidazolium acetate was added to the cellulosic suspension. After five minutes stirring at 100 ° C, a clear cellulose solution was obtained.
  • Vicel ® microcrystalline cellulose
  • microcrystalline cellulose (Avicel ®) were added with stirring at 100 ° C to 5 ml of 1-methyl-2-pyrrolidinone. Subsequently, to the cellulose suspension 1, 6 ml of 1-ethyl-3-methylimidazolium acetate was added. Immediately a clear cellulose solution was obtained.
  • microcrystalline cellulose 0.5 g was added with stirring at 100 ° C to a mixture of 5 ml of 1-methyl-2-pyrrolidinone and 1.6 ml of 1-ethyl-3-methylimidazolium acetate. The cellulose had dissolved with stirring at 100 ° C after 2 minutes.
  • microcrystalline cellulose 0.5 g was added with stirring at 100 ° C to 5 ml of N, N-dimethylformamide. Then, with stirring, 1.2 ml of 1-ethyl-3-methylimidazolium acetate were added to the cellulosic suspension. Immediately a clear cellulose solution was obtained.
  • microcrystalline cellulose (Avicel ®) were added to 5 ml of 1, 1, 3,3-tetramethylurea with stirring at 100 ° C. Subsequently, 5 ml of 1-ethyl-3-methylimidazolium acetate were added to the cellulosic suspension. After stirring at 100 ° C. for five minutes, a clear cellulose solution was obtained.
  • microcrystalline cellulose 0.5 g was added to 5 g of molten ⁇ -valerolactam with stirring at 100 ° C. Subsequently, 3 ml of 1-ethyl-methylimidazoliumacetat were added to the cellulose solution. A clear solution was obtained in less than one minute with stirring at 100 ° C.
  • EXAMPLE 14 0.5 g of microcrystalline cellulose (Avicel) was added in 5 g of molten ⁇ -caprolactam with stirring at 100 ° C. Subsequently, 3.5 ml of 1-ethyl-3-methylimidazolium acetate was added to the cellulosic suspension. Within one minute with stirring at 100 ° C gave a clear solution.
  • microcrystalline cellulose (Avicel ®, Aldrich) were added with stirring at 100 ° C to 20 ml of 1, 3-dimethyl-2-imidazolidinone. Subsequently, 20 g of 1-butyl-3-methylimidazolium chloride (BMIMCI) was added to the cellulosic suspension. Immediately with stirring at 100 ° C., a clear cellulose solution was obtained (10% Avicel - BMIMCI-dimethylimidazolidone [1: 1]). 4 g of microcrystalline cellulose (Avicel ®, Aldrich) were added 1-butyl-3-methylimidazolium chloride with stirring at 100 ° C to 40 g. After seven hours stirring at 100 ° C, a cellulose solution was obtained (10% Avicel - BMIMCI).
  • BMIMCI 1-butyl-3-methylimidazolium chloride
  • microcrystalline cellulose (Avicel ®) were added with stirring at 100 ° C to 5 g of 1, 3- dimethyl-2-imidazolidinone. Subsequently, 1.62 g of 1-ethyl-3-methylimidazolium acetate were added to the cellulosic suspension. It spontaneously formed a clear cellulose solution with stirring at 100 ° C. After cooling (about 80 ° C) have two phases are formed. The upper phase consists of 1, 3-dimethyl-2-imidazolidinone and also contains 1-ethyl-3-methylimidazolium acetate, while the lower phase is a solution of cellulose in 1-ethyl-3-methylimidazolium acetate.
  • cellulose (Avicel ®) were added imidazolidinone with stirring at 100 ° C to 5.25 g of 1, 3-dimethyl-2-. Subsequently, 1.72 g of 1-ethyl-3-methylimidazolium acetate was added to the cellulosic suspension. It spontaneously formed a clear cellulose solution with stirring at 100 ° C. After cooling (about 40 ° C) have two phases are formed. The upper phase consists of 1, 3-dimethyl-2-imidazolidinone and also contains 1-ethyl-3-methylimidazolium acetate, while the lower phase is a solution of cellulose in 1-ethyl-3-methylimidazoliumacetat.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Paper (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

L'invention concerne un procédé pour dissoudre de la cellulose, selon lequel une matière cellulosique est mise en suspension dans un solvant aprotique polaire et au moins un sel organique ou inorganique est ajouté à la suspension obtenue. La matière cellulosique se dissous presque spontanément, c'est-à-dire dès l'ajout de sel.
PCT/DE2011/075145 2010-06-23 2011-06-21 Procédé pour dissoudre de la cellulose Ceased WO2012022325A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102010024827A DE102010024827A1 (de) 2010-06-23 2010-06-23 Verfahren zum Auflösen von Zellulose
DE102010024827.4 2010-06-23

Publications (2)

Publication Number Publication Date
WO2012022325A2 true WO2012022325A2 (fr) 2012-02-23
WO2012022325A3 WO2012022325A3 (fr) 2012-06-14

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PCT/DE2011/075145 Ceased WO2012022325A2 (fr) 2010-06-23 2011-06-21 Procédé pour dissoudre de la cellulose

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WO (1) WO2012022325A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114622407A (zh) * 2022-04-01 2022-06-14 浙江隆腾医用新材料有限公司 一种羧甲基纤维素钠纤维的洗脱方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US943176A (en) 1908-08-08 1909-12-14 Joseph Henry Burdock Light-extinguisher.
WO2003029329A2 (fr) 2001-10-03 2003-04-10 The University Of Alabama Dissolution et traitement de cellulose au moyen de liquides ioniques
WO2007057235A2 (fr) 2005-04-15 2007-05-24 Basf Aktiengesellschaft Solutions de cellulose dans des liquides ioniques
US20090088564A1 (en) 2007-09-28 2009-04-02 Weyerhaeuser Company Dissolution of Cellulose in Mixed Solvent Systems

Family Cites Families (8)

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Publication number Priority date Publication date Assignee Title
US4302252A (en) * 1979-07-25 1981-11-24 International Telephone And Telegraph Corp. Solvent system for cellulose
DE102005017733A1 (de) * 2005-04-15 2006-10-19 Basf Ag Löslichkeit von Cellulose in ionischen Flüssigkeiten unter Zugabe von Aminbase
DE102005062608A1 (de) * 2005-12-23 2007-07-05 Basf Ag Lösungssystem auf der Basis geschmolzener ionischer Flüssigkeiten ein Verfahren zu dessen Herstellung sowie zur Herstellung regenerierter Kohlenydrate
DE102006035830A1 (de) * 2006-08-01 2008-02-07 Basf Ag Lösungssystem auf der Basis geschmolzener ionischer Flüssigkeiten, dessen Herstellung sowie Verwendung zur Herstellung regenerierter Kohlenhydrate
US7674608B2 (en) * 2007-02-23 2010-03-09 The University Of Toledo Saccharifying cellulose
EP2062922A1 (fr) * 2007-11-14 2009-05-27 Basf Se Procédé de fabrication de biopolymères régénérés et résultats régénérés obtenus ensuite
EP2303825B1 (fr) * 2008-06-17 2016-11-09 Wisconsin Alumni Research Foundation Transformation chimique de biomasse lignocellulosique en combustibles et produits chimiques
EP2157103A1 (fr) * 2008-08-18 2010-02-24 BIOeCON International Holding N.V. Procédé de régénération ou dérivatisation de cellulose

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US943176A (en) 1908-08-08 1909-12-14 Joseph Henry Burdock Light-extinguisher.
WO2003029329A2 (fr) 2001-10-03 2003-04-10 The University Of Alabama Dissolution et traitement de cellulose au moyen de liquides ioniques
WO2007057235A2 (fr) 2005-04-15 2007-05-24 Basf Aktiengesellschaft Solutions de cellulose dans des liquides ioniques
US20090088564A1 (en) 2007-09-28 2009-04-02 Weyerhaeuser Company Dissolution of Cellulose in Mixed Solvent Systems

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114622407A (zh) * 2022-04-01 2022-06-14 浙江隆腾医用新材料有限公司 一种羧甲基纤维素钠纤维的洗脱方法
CN114622407B (zh) * 2022-04-01 2023-09-19 浙江隆腾医用新材料有限公司 一种羧甲基纤维素钠纤维的洗脱方法

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Publication number Publication date
WO2012022325A3 (fr) 2012-06-14
DE102010024827A1 (de) 2011-12-29

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