CN101037479B - Method for dissolving cellulos - Google Patents
Method for dissolving cellulos Download PDFInfo
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- CN101037479B CN101037479B CN200710051867A CN200710051867A CN101037479B CN 101037479 B CN101037479 B CN 101037479B CN 200710051867 A CN200710051867 A CN 200710051867A CN 200710051867 A CN200710051867 A CN 200710051867A CN 101037479 B CN101037479 B CN 101037479B
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Abstract
The invention discloses a method for dissolving the cellulose, including having the sodium hydroxide and urea as material, firstly pre-cooling the 12-20 wt.% of sodium hydroxide water solution to -4-10 DEG C, adding cellulose to produce an alkaline cellulase, or mixing the cellulase and 12-20 wt.% of sodium hydroxide water solution, mixing and pre-cooling to -4-10 DEG C to produce an alkaline cellulase, than adding -4-10 DEG C 0-40 wt.% urea water solution, blending uniformly, immediately getting the transparent cellulose solution. The method can swiftly dissolve the natural cellulose with a molecular weight under 13*104 and the II-type cellulose with a molecular weight under 15*104 and may obtain a dense cellulose solution with a high solubility (100%).
Description
Technical field
The present invention relates to a kind of method of dissolving cellulos.
Background technology
Enter 21st century, Science and Technology has turned to the starting material of the renewable resources and the energy, and the technology of environment-friendly material and Sustainable development and process.Plant cellulose is a renewable resources the abundantest on the earth, belongs to environment-friendly material, makes full use of Mierocrystalline cellulose and not only can protect environment, and can save limited petroleum resources.Yet the cellulose dissolution process is numerous and diverse in the existing at present cellulose industry, cost is high and pollution is arranged.The viscose process that is still of heavy industrialization is produced artificial silk and glassine paper so far, produces a large amount of CS in the production process
2And serious environment pollution.Producing copper rayon with cuprammonium process also exists environmental pollution, costs an arm and a leg and solution recovery problem.Other organic or inorganic solvents, for example: methyl-sulphoxide-oxynitride (U.S.patent 3236669,1966), ZnCl
2The aqueous solution (U.S.Patent 5290349,1994), LiCl/DMAc (U.S.Patent 4302252,1981) etc. are difficult to industrialization owing to dissolution process is numerous and diverse with price problem.Novel solvent N-methyl morpholine oxide (NMMO) (U.S.patent2179181,1939 have appearred in recent years; Brit.1144048,1967; U.S.patent 4246221,1981), and be considered to the most promising cellosolve, but owing to it costs an arm and a leg, the temperature of dissolving cellulos is higher, suitability for industrialized production is made slow progress.Equally, ionic liquid also is used for dissolving cellulos, but still exists high-temperature digestion and solvent to need problems such as recovery fully.In addition, Mierocrystalline cellulose and urea at high temperature react the generation cellulose carbamate, directly are dissolved in then and obtain spinning solution (Finnish Patent 61003 in the sig water; FinnishPatent 62318; U.S.Patent 4404369), but the amount of urea height, by product is arranged, also be difficult to industrialization.Japan reports (Japan Patent 1777283,1983; U.S.Patent 4634470) at 2.5molL
-1Dissolving cellulos in the NaOH aqueous solution, but must use the wood pulp cellulose of handling through steam explosion (polymerization degree is lower than 250).The solvent compositions that Chinese patent 00114486.3 discloses a kind of dissolving cellulos is used for cellulosic dissolving, and this solvent compositions can only dissolve the less Mierocrystalline cellulose of molecular weight and (be lower than 8.5 * 10
4), and dissolution time long (more than 12 hours), solubleness is less, so industrialization is very limited.
Summary of the invention
The method that the purpose of this invention is to provide the lower dissolving cellulos of a kind of energy consumption, but this method dissolving cellulos within a short period of time, solubleness is higher, is easy to industrialization.
For achieving the above object, the technical solution adopted in the present invention is as follows:
A kind of method of dissolving cellulos, Mierocrystalline cellulose is dispersed in 12～20wt%NaOH aqueous solution, be chilled to-4～10 ℃ in advance, the generation soda cellulose that stirs adds 0～40wt% aqueous solution of urea of-4～25 ℃ again, and stirring under 0～25 ℃ makes transparent cellulose solution, content of cellulose is 2～8wt% in the cellulose solution that makes, NaOH content is 4.8～12wt%, and urea content is 0～24wt%, and all the other are water.
Perhaps, 12～20wt%NaOH aqueous solution is chilled to-4～10 ℃ in advance, adds the Mierocrystalline cellulose generation soda cellulose that stirs, add 0～40wt% aqueous solution of urea of-4～25 ℃ then, stirring under 0～25 ℃ makes transparent cellulose solution; Content of cellulose is 2～8wt% in the cellulose solution that makes, and NaOH content is 6～10%, and urea content is 0～20%, and all the other are water.
The consumption mass ratio of above-mentioned Mierocrystalline cellulose, 12～20wt%NaOH aqueous solution and 0～40wt% aqueous solution of urea is: 2～8: 40～60: 40～60.
The present invention can be used for industrial dissolving cellulos, prepares various cellulose silks, film, non-woven fabrics and chromatographic column protruded packing.Also can be used on the laboratory and carry out the research of molecular weight cellulose and SOLUTION PROPERTIES.Cellulose membrane of the present invention can be used as textiles, plastic sheeting for farm use, packing and the parting material in the fields such as textile industry, agricultural, chemical industry, food, environment.
Compared with the prior art, innovation of the present invention is as follows:
The present invention adopts at first the pretreatment of fiber rope to generate soda cellulose, adds the method for entry or aqueous solution of urea again and reaches the purpose of rapid dissolving cellulos.Temperature range is wide and gentle in dissolution process, and dissolving total time has obviously been reduced energy consumption in 10 minutes.The concentration range of sodium hydroxide and urea is than broad in the final solution, and concentration is respectively 6～10wt% and 0～20wt%.And the solubleness of various Mierocrystalline celluloses (cotton linter pulp, straw fiber slurry, bagasse pulp, wood pulp and cellulosic nonwoven fabric and steam quick-fried cellulose slurry etc.) all reached 100%, can make the strong solution of higher molecular weight.There are not other severe condition, not high to equipment requirements, help suitability for industrialized production.
The present invention is a raw material with sodium hydroxide, urea, water, and low price is simple to operation, environmentally safe.And the dissolving and regeneration all be physical process, chemical reaction does not take place, the easy recycling use of waste liquid.
Embodiment
Below in conjunction with concrete example technical scheme of the present invention is described further:
Embodiment 1
Get regenerated cellulose (non-woven fabrics M
η=15 * 10
4) 10 grams, add in the 95 gram 14wt%NaOH aqueous solution, stirred 5 minutes, be placed on then and be chilled to 0 ℃ in the refrigerator in advance, taking-up stirs, and adds the 20wt% aqueous solution of urea of 5 ℃ of 95 grams, makes transparent cellulose solution after at room temperature (25 ℃) stir.The total time of dissolving cellulos, dissolution rate was very fast in 10 minutes.Content of cellulose is 5wt% in the cellulose solution that makes, and NaOH content is about 7wt%, and urea content is about 10wt%, and all the other are water.
Embodiment 2
The 90 gram 20wt%NaOH aqueous solution are chilled to 10 ℃ in advance in refrigerator, get cotton linter pulp (viscosity-average molecular weight M immediately
η=8 * 10
4) 8 grams drop into wherein, stir (about 3 minutes), add the water of 10 ℃ of 102 grams then rapidly, at room temperature (25 ℃) back (about 5 minutes) that stirs makes transparent cellulose solution.Dissolving cellulos speed is very fast, and dissolved total time is in 10 minutes.Content of cellulose is 4wt% in the cellulose solution that makes, and NaOH content is 9wt%, and all the other are water.
Embodiment 3
The 100 gram 12wt%NaOH aqueous solution are chilled to-4 ℃ in advance in refrigerator, get cotton linter pulp (viscosity-average molecular weight M immediately
η=6 * 10
4) 10 grams drop into wherein, stir (about 4 minutes), add the 40wt% aqueous solution of urea of 15 ℃ of 90 grams then rapidly, at room temperature (25 ℃) back (about 5 minutes) that stirs makes transparent cellulose solution.Dissolving cellulos speed is very fast, and dissolved total time is in 10 minutes.Content of cellulose is 5wt% in the cellulose solution that makes, and NaOH content is 6wt%, and urea content is 18wt%, and all the other are water.
Embodiment 4
The 90 gram 16wt%NaOH aqueous solution are chilled to 0 ℃ in advance in refrigerator, get wood pulp cellulose (viscosity-average molecular weight M immediately
η=6 * 10
4) 10 grams drop into wherein, stir (about 3 minutes), add the 24wt% aqueous solution of urea of 15 ℃ of 100 grams then rapidly, at room temperature (25 ℃) back (about 5 minutes) that stirs makes transparent cellulose solution.Dissolving cellulos speed is very fast, and dissolved total time is in 10 minutes.Content of cellulose is 5wt% in the cellulose solution that makes, and NaOH content is about 8wt%, and urea content is 12wt%, and all the other are water.
Embodiment 5
The 100 gram 20wt%NaOH aqueous solution are chilled to 0 ℃ in advance in refrigerator, get wood pulp cellulose (viscosity-average molecular weight M immediately
η=6 * 10
4) 16 grams drop into wherein, stir (about 3 minutes), add the 24wt% aqueous solution of urea of 15 ℃ of 84 grams then rapidly, at room temperature (25 ℃) back (about 5 minutes) that stirs makes transparent cellulose solution.Dissolving cellulos speed is very fast, and dissolved total time is in 10 minutes.Content of cellulose is 8wt% in the cellulose solution that makes, and NaOH content is 10wt%, and urea content is about 10wt%, and all the other are water.
Embodiment 6
The 97 gram 14wt%NaOH aqueous solution are chilled to 0 ℃ in advance in refrigerator, get cotton linter pulp (viscosity-average molecular weight M immediately
η=13 * 10
4) 8 grams drop into wherein, stir (about 2 minutes), add the 20wt% aqueous solution of urea of 5 ℃ of 95 grams then rapidly, at room temperature (25 ℃) back (about 5 minutes) that stirs makes transparent cellulose solution.Dissolving cellulos speed is very fast, and dissolved total time is in 10 minutes.Content of cellulose is 4wt% in the cellulose solution that makes, and NaOH content is about 7wt%, and urea content is about 10wt%, and all the other are water.
With after making transparent cellulose solution evacuation and centrifugal degassing and removing on a small quantity not fibrinolysin on sheet glass casting film-forming, put into the 5wt% aqueous sulfuric acid then, soak after 5 minutes and take out, water is rinsed well.Be attached at last that natural airing obtains regenerated cellulose film on the sheet glass.Record its tensile strength σ by electronics pulling experiment machine
b, elongation at break ε
bAnd Young's modulus is respectively 95MPa, 12% and 5000MPa.Transmittance is 88% (400-800nm).
Claims (4)
1. the method for a dissolving cellulos, it is characterized in that: Mierocrystalline cellulose is dispersed in 12～20wt%NaOH aqueous solution, be chilled to 0 to 10 ℃ in advance, the generation soda cellulose that stirs adds 0～40wt% aqueous solution of urea of 5 to 25 ℃ again, and stirring under 0～25 ℃ makes transparent cellulose solution, content of cellulose is 2～8wt% in the cellulose solution that makes, NaOH content is 4.8～12wt%, and urea content is 0～24wt%, and all the other are water.
2. method according to claim 1 is characterized in that: the consumption mass ratio of Mierocrystalline cellulose, 12～20wt%NaOH aqueous solution and 0～40wt% aqueous solution of urea is: 2～8: 40～60: 40～60.
3. the method for a dissolving cellulos, it is characterized in that: 12～20wt%NaOH aqueous solution is chilled to 0 to 10 ℃ in advance, add the Mierocrystalline cellulose generation soda cellulose that stirs, 0～40wt% the aqueous solution of urea that adds 5 to 25 ℃ then, stirring under 0～25 ℃ makes transparent cellulose solution; Content of cellulose is 2～8wt% in the cellulose solution that makes, and NaOH content is 6～10%, and urea content is 0～20%, and all the other are water.
4. method according to claim 3 is characterized in that: the consumption mass ratio of Mierocrystalline cellulose, 12～20wt%NaOH aqueous solution and 0～40wt% aqueous solution of urea is: 2～8: 40～60: 40～60.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710051867A CN101037479B (en) | 2007-04-13 | 2007-04-13 | Method for dissolving cellulos |
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| CN200710051867A CN101037479B (en) | 2007-04-13 | 2007-04-13 | Method for dissolving cellulos |
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| CN101037479A CN101037479A (en) | 2007-09-19 |
| CN101037479B true CN101037479B (en) | 2010-05-19 |
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| CN200710051867A Expired - Fee Related CN101037479B (en) | 2007-04-13 | 2007-04-13 | Method for dissolving cellulos |
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Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102191706A (en) * | 2010-03-19 | 2011-09-21 | 上海市七宝中学 | Process for preparing cellulose |
| CN102432891B (en) * | 2011-09-15 | 2014-02-12 | 南华大学 | Method for dissolving cellulose |
| CN102504299B (en) * | 2011-09-30 | 2013-12-25 | 江南大学 | Preparation method for regenerated cellulose/epoxy resin composite film |
| CN102492163A (en) * | 2011-12-27 | 2012-06-13 | 武汉大学 | Preparation method of high-hydrophobicity cellulose membrane |
| CN103103663B (en) * | 2012-11-29 | 2016-03-30 | 宁波双盾纺织帆布实业有限公司 | A kind of gas spinning method of fibre and soya |
| CN103060937B (en) * | 2013-01-29 | 2015-06-10 | 武汉大学 | Preparation method of cellulose nanofiber |
| CN104480722B (en) * | 2014-12-24 | 2017-02-22 | 东华大学 | Non-slurry self-sizing method for cellulosic fiber containing yarns |
| CN105136892B (en) * | 2015-09-06 | 2017-12-12 | 广东南海普锐斯科技有限公司 | A kind of electrochemical sensor cellulose heteropoly acid PEM and its preparation method |
| CN105185939A (en) * | 2015-09-22 | 2015-12-23 | 武汉惠强新能源材料科技有限公司 | Lithium ion battery separator with low thermal shrinkage rate and preparation method therefor |
| CN106749726B (en) * | 2016-12-13 | 2018-12-25 | 广西壮族自治区农业科学院农产品加工研究所 | A method of extracting Arillus longan polysaccharide |
| CN109610024B (en) * | 2018-11-20 | 2020-02-18 | 华南理工大学 | Cellulose-molybdenum disulfide aerogel composite fiber and preparation method and application thereof |
| CN110409224A (en) * | 2019-06-10 | 2019-11-05 | 浙江金昌特种纸股份有限公司 | A kind of preparation method of cellulose coating lithium ion battery diaphragm |
| CN111809260B (en) * | 2020-06-24 | 2023-09-01 | 湖北金环新材料科技有限公司 | Recycling method of waste adhesive film |
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| DE3247776A1 (en) * | 1982-12-23 | 1984-06-28 | Hoechst Ag, 6230 Frankfurt | Method for dissolving cellulose |
| CN1377895A (en) * | 2002-04-09 | 2002-11-06 | 武汉大学 | Process for preparing hydroxy ethyl cellulose |
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| WO2004046198A1 (en) * | 2002-11-18 | 2004-06-03 | Zimmer Ag | Method for the production of cellulose carbamate in an inert organic reaction medium |
| CN1594680A (en) * | 2004-06-29 | 2005-03-16 | 武汉大学 | Preparation method for regenerated cellulose fiber |
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2007
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| CN1377895A (en) * | 2002-04-09 | 2002-11-06 | 武汉大学 | Process for preparing hydroxy ethyl cellulose |
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Non-Patent Citations (6)
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