CN102432891A - Method for dissolving cellulose - Google Patents
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- CN102432891A CN102432891A CN2011102730503A CN201110273050A CN102432891A CN 102432891 A CN102432891 A CN 102432891A CN 2011102730503 A CN2011102730503 A CN 2011102730503A CN 201110273050 A CN201110273050 A CN 201110273050A CN 102432891 A CN102432891 A CN 102432891A
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Abstract
The invention discloses a method for dissolving cellulose, characterized by: using at least one from the group consisting of wood pulp, cotton pulp, hemp pulp, bamboo pulp, bagasse pulp, grass fibered pulp, cellulose non-woven fabric or steam exploded cellulose pulp as cellulose raw material, uniformly stirring the cellulose raw material, NaOH and water at a temperature of -15-50 DEG C to obtain a cellulose solution. The prepared cellulose concentrated solution has good spinnability and film forming property. The method breaks through a dissolution method of traditional gluing technology, does not relate to carbon disulfide and other substance causing serious environmental pollution, and is green and environmentally friendly. According to the invention, the cellulose raw material can be directly rapidly dissolved at room temperature, without heating or precooling a solvent. The method has the advantages of saving energy, and reducing energy consumption. By using raw materials having low cost, the method has the advantages of simple operation, small investment, high productivity, and is easy to realize large-scale industrial production.
Description
Technical field
The present invention relates to a kind of cellulosic dissolving method, belong to the natural polymer chemical category.
Background technology
Renewable resources, Sustainable development technology and environment-friendly material have become the important directions of 21st century science and technology research and development.Plant cellulose is the abundantest renewable resources of the earth, belongs to the environmental friendliness macromolecular material, and is expected one of main industrial chemicals that becomes 21 century.Mierocrystalline cellulose can be widely used in technical fields such as weaving, papermaking, tobacco, food, agricultural and petrochemical complex.The whole world be used to the to weave Mierocrystalline cellulose of papermaking just reaches 8,000,000 tons every year.But present regenerated cellulose product more than 90% still adopts traditional viscose process production, like J.Macromol.Sci.-Rev.Macromol.Chem., and 1980, C18 (1), the method that adopts in 1 is, Mierocrystalline cellulose is under the highly basic effect and CS
2Reaction generates cellulose xanthate, after be dissolved in dilute alkaline soln and prepare viscose.The Mierocrystalline cellulose viscose is regenerated in dilute acid soln after spray silk or curtain coating, makes viscose fiber or zellglas.This method discharges a large amount of poisonous CS in process of production
2And H
2S gas not only damages HUMAN HEALTH, and serious environment pollution.Producing the cuprammonium regenerated fiber with cuprammonium process exists environmental pollution and solution to reclaim problem.Other organic or inorganic solvents, for example: methyl-sulphoxide-oxynitride (U.S.patent 3236669,1966), NH
3/ NH
4The SCN aqueous solution (J.Polym.Sci.Polym.Chem.Ed., 1980,18,3469), Ca (SCN)
2/ NaSCN the aqueous solution (Polymer J., 1998,30,43:30,49), ZnCl
2The aqueous solution (U.S.Patent5290349,1994), trichoro-aldehyde one methyl-sulphoxide, one pyridine mixed solution (Polym.J1980,12,521), LiCl/DMAc (U.S.Patent 4302252,1981) etc. do not see industrialization for various reasons so far.N-methyl morpholine oxide (MMNO) (J.Polym.Sci.:Polym.Lett.Ed.1979,17,219) once was acknowledged as the most promising cellosolve.1978, German Akzo Nobel company at first obtained its cellulosic fibre solvent-spinning method patent, and obtained the production technique patent in 1980.The international Zantrel in Brussels in 1989 and the synthon Bureau of Standards (BISFA) are the category name of the cellulosic fibre of being made by these class methods " Lyocell ".After this, the small amount of fibers cellulose fiber product with its preparation comes into the market in the world, but because solvent costs an arm and a leg, spinning temperature is higher, the suitability for industrialized production slower development.In addition, reported that Mierocrystalline cellulose and urea at high temperature react the generation cellulosecarbamate, directly be dissolved in then and obtain spinning solution (Finnish Patent 61003 in the sig water; Finnish Patent 62318; U.S.Patent4404369), but amount of urea is high, and also has by product, is difficult to industrialization.Also reported at present the method for the dissolving cellulos that some are environmentally friendly, wherein a kind of be with cellulose dissolution in precooling solvent extremely, this method time spent is short; Efficient is high, and pollution-free and cheap, used solvent is nontoxic and recyclable to be recycled; Therefore be a kind of green production process, but this method is can loss-rate big, need be as dissolving 42 kilograms of Mierocrystalline celluloses at precooling 1 ton of solvent nearly; Not only bad for energy-saving consumption-reducing, and be difficult to industrialized production.People such as Kamide have reported that Mierocrystalline cellulose is at 2.5molL
-1Dissolving in the NaOH aqueous solution, but this solvent must use the polymerization degree to be lower than 250 the wood pulp cellulose of handling through steam explosion, and it is dissolvable in water (Japan Patent1777283,1983 in the NaOH solution when 4 ℃ of left and right sides; U.S.Patent 4634470:Polymer J., 1984,12,857; Polymer J., 1988,20,447), and obtained fiber yarn intensity is extremely low.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 industriallization is very limited.
Summary of the invention
The objective of the invention is to overcome the problem that exists in the above-mentioned existing cellulose dissolution method, a kind of dissolving cellulos efficient height, method environmental protection, energy-saving consumption-reducing are provided and are easy to realize the method for industrialized production.
Realize that the technical scheme that the object of the invention adopted is following:
A kind of method of dissolving cellulos; With wood pulps, the cotton pulp dregs of rice, hemp dissolving pulp, bamboo pulp, bagasse pulp, straw fiber slurry, cellulosic nonwoven fabric or to steam at least a in the quick-fried cellulose slurry be cellulosic material; Cellulosic material, NaOH and water stirred under-15-50 ℃ promptly make transparent cellulose solution; Content of cellulose is 2-8wt% in the cellulose solution that makes, and NaOH content is 5～12wt%, and all the other are water.
Perhaps with cellulosic material, NaOH, water, and urea stirs under-15-50 ℃, promptly makes transparent cellulose solution; Content of cellulose is 2-8wt% in the cellulose solution that makes; NaOH content is 5～12wt%, and urea content is no more than 18wt%, and all the other are water.
Perhaps earlier cellulosic material being dispersed in concentration is no more than in the urea soln of 18wt%; Under-15-50 ℃, stir, adding NaOH or concentration then is 6-12wt%NaOH solution, continues under-15-50 ℃, to stir to make transparent cellulose solution; Content of cellulose is 2-8wt% in the cellulose solution that makes; NaOH content is 5～12wt%, and urea content is no more than 18wt%, and all the other are water.
Perhaps earlier NaOH and water are processed the NaOH solution that concentration is 6-12wt%; Cellulosic material is dispersed in the NaOH solution, under-15-50 ℃, stirring makes cellulose solution again, and content of cellulose is 2-8wt% in the cellulose solution that makes; NaOH content is 5～12wt%, and all the other are water.
Perhaps earlier cellulosic material is dispersed in the NaOH solution that concentration is 6-12wt%; Under-15-50 ℃, stir, add the urea soln that urea or concentration are no more than 18wt% then, continuing under-15-50 ℃, to stir makes transparent cellulose solution; Content of cellulose is 2-8wt% in the cellulose solution that makes; NaOH content is 5～12wt%, and urea content is no more than 18wt%, and all the other are water.
Can know by technique scheme; It is solvent that the present invention comes down to adopt NaOH solution; Be main solvent perhaps with NaOH solution; Urea soln is a secondary solvent, through the amount ratio between strictness control solute Mierocrystalline cellulose and solvent, thereby makes cellulosic material under room temperature, directly be dissolved in the Mierocrystalline cellulose strong solution that makes high-dissolvability in the solvent fast.As solvent, directly the solvent polymerization degree is up to 550 Mierocrystalline cellulose with low-cost sodium hydroxide and urea soln for this method.
The present invention can be used for industry and goes up dissolving cellulos, is used for papermaking or 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 present technology, advantage of the present invention is following:
The present invention adopts sodium hydroxide solution or sodium hydroxide and urea mixing solutions as the at room temperature directly quick dissolving cellulos of solvent.Temperature is-normal room temperature of 15-50 ℃ in dissolution process, need not the precooling solvent, has obviously reduced energy consumption.The concentration of sodium hydroxide, urea is respectively 5-12wt% and is no more than 18wt% in the final solution, and concentration range is also within reason narrow, satisfies industrial requirements easily.And as long as the dissolving of comparing various Mierocrystalline celluloses (wood pulps, bamboo pulp, hemp dissolving pulp, cotton linter pulp, straw fiber slurry, bagasse pulp and cellulosic nonwoven fabric and steam quick-fried cellulose slurry etc.) according to amount of the present invention can both reach 100% dissolving fully; Can make the strong solution of higher molecular weight (mean polymerisation degree up to 550 Mierocrystalline cellulose); And dissolution rate is very fast, soon then several minutes, then can fully dissolve in the several hrs slowly.Method provided by the invention can use the common equipment of traditional adhering process to accomplish, and is very beneficial for realizing industrialized production.
The present invention is simple to operation, the low price of material therefor sodium hydroxide, urea, water, environmentally safe.And related dissolving and regeneration all is physical process in the method provided by the invention, and any chemical reaction does not take place, and the solvent easy recovery recycles, and further reduces production costs.
The present invention is direct dissolving cellulos at room temperature, obtains the Mierocrystalline cellulose strong solution of spinning property and good film-forming property.Dissolved efficiency height of the present invention, method environmental protection, energy-saving consumption-reducing and be easy to realize the method for industrialized production.
Embodiment
Below in conjunction with concrete embodiment technical scheme of the present invention is described further:
Embodiment 1
Under 45 ℃ of room temperatures; With the cotton pulp dregs of rice or bamboo pulp, bagasse pulp, straw fiber slurry, the cellulosic nonwoven fabric of 5g or steam in the 8wt%NaOH solution of a kind of 90g of joining in the quick-fried cellulose slurry and fully stirred 2 hours rapidly; Again to wherein adding 5g urea; Stir half a hour down at 45 ℃, can obtain cellulose solution.Content of cellulose is 5wt% in the cellulose solution that makes, and NaOH content is about 7.2wt%, and urea content is 5wt%, and all the other are water.
Embodiment 2
Under 20 ℃ of room temperatures; With wood pulps, the cotton pulp dregs of rice, hemp dissolving pulp, bamboo pulp, bagasse pulp, straw fiber slurry, the cellulosic nonwoven fabric of 6g or steam in the 12wt%NaOH solution of a kind of 80g of joining in the quick-fried cellulose slurry and fully stirred 1 hour rapidly; Again to wherein adding 14g urea; Stirred one hour down at 20 ℃, can obtain cellulose solution.Content of cellulose is 6wt% in the cellulose solution that makes, and NaOH content is about 9.6wt%, and urea content is about 14wt%, and all the other are water.
Embodiment 3
Under 15 ℃ of room temperatures, the hemp dissolving pulp of 2g is joined in the 10wt%NaOH solution of 58g and stirred 0.5 hour rapidly, again to the 18wt% urea that wherein adds 40g, stirred one hour down at 15 ℃, can obtain transparent cellulose solution.Content of cellulose is 2wt% in the cellulose solution that makes, and NaOH content is about 5.8wt%, and urea content is about 7.2wt%, and all the other are water.
Embodiment 4
Under 4 ℃ of room temperatures; With wood pulps, the cotton pulp dregs of rice, hemp dissolving pulp, bamboo pulp, bagasse pulp, straw fiber slurry, the cellulosic nonwoven fabric of 8g or steam in the quick-fried cellulose slurry one or more join 80g as raw material the 12wt%NaOH solution and stirred 2 hours rapidly; Again to wherein adding 12g urea; Stirred one hour down at 4 ℃, can obtain the vitreous fibre cellulose solution.Content of cellulose is 8wt% in the cellulose solution that makes, and NaOH content is 9.6wt%, and urea content is 7.2wt%, and all the other are water.
Embodiment 5
Under 25 ℃ of room temperatures, bamboo pulp and the 8g NaOH of 6g mixed, add 74mL water, stir half a hour rapidly, to wherein adding 12g urea, stirred one hour down again at 25 ℃, can obtain transparent cellulose solution.Content of cellulose is 6wt% in the cellulose solution that makes, and NaOH content is about 8wt%, and urea content is about 12wt%, and all the other are water.
Embodiment 6
Under 5 ℃ of room temperatures, the cotton pulp dregs of rice and the 12g urea of 6g is mixed, add 74mL water, stir half a hour rapidly, to wherein adding 8gNaOH, stirred one hour down again at 5 ℃, can obtain transparent cellulose solution.Content of cellulose is 6wt% in the cellulose solution that makes, and NaOH content is about 8wt%, and urea content is about 12wt%, and all the other are water.
Embodiment 7
Under 5 ℃ of room temperatures, the cotton pulp dregs of rice and the 8g NaOH of 5g mixed, add 87mL water, stirred rapidly one hour, can obtain cellulose solution.Content of cellulose is 5wt% in the cellulose solution that makes, and NaOH content is about 8wt%, and all the other are water.
Embodiment 8
Under 25 ℃ of room temperatures; With wood pulps, the cotton pulp dregs of rice, hemp dissolving pulp, bamboo pulp, bagasse pulp, straw fiber slurry, the cellulosic nonwoven fabric of 5g or steam in the 8wt%NaOH solution of a kind of 95g of adding in the quick-fried cellulose slurry; Stirred one hour rapidly, can obtain cellulose solution.Content of cellulose is 5wt% in the cellulose solution that makes, and NaOH content is about 7.6wt%, and all the other are water.
The foregoing description all can carry out under-15 ℃-0 ℃.
Claims (5)
1. cellulosic dissolving method; It is characterized in that: with wood pulps, the cotton pulp dregs of rice, hemp dissolving pulp, bamboo pulp, bagasse pulp, straw fiber slurry, cellulosic nonwoven fabric or to steam at least a in the quick-fried cellulose slurry be cellulosic material; Cellulosic material, NaOH and water stirred under-15-50 ℃ promptly make transparent cellulose solution; Content of cellulose is 2-8wt% in the cellulose solution that makes, and NaOH content is 5～12wt%, and all the other are water.
2. according to the said cellulosic dissolving method of claim 1; It is characterized in that: with cellulosic material, NaOH, water, and urea stirs under-15-50 ℃, promptly makes transparent cellulose solution; Content of cellulose is 2-8wt% in the cellulose solution that makes; NaOH content is 5～12wt%, and urea content is no more than 18wt%, and all the other are water.
3. according to the said cellulosic dissolving method of claim 2, it is characterized in that: earlier cellulosic material being dispersed in concentration is no more than in the urea soln of 18wt%, under-15-50 ℃, stirs; Adding NaOH or concentration then is 6-12wt%NaOH solution; Continuation stirs under-15-50 ℃ and makes transparent cellulose solution, and content of cellulose is 2-8wt% in the cellulose solution that makes, and NaOH content is 5～12wt%; Urea content is no more than 18wt%, and all the other are water.
4. according to the said cellulosic dissolving method of claim 1; It is characterized in that: earlier NaOH and water are processed the NaOH solution that concentration is 6-12wt%; Cellulosic material is dispersed in the NaOH solution, under-15-50 ℃, stirring makes cellulose solution again, and content of cellulose is 2-8wt% in the cellulose solution that makes; NaOH content is 5～12wt%, and all the other are water.
5. according to the said cellulosic dissolving method of claim 4, it is characterized in that: earlier cellulosic material is dispersed in the NaOH solution that concentration is 6-12wt%, under-15-50 ℃, stirs; Add urea or concentration then and be no more than the urea soln of 18wt%; Continuation stirs under-15-50 ℃ and makes transparent cellulose solution, and content of cellulose is 2-8wt% in the cellulose solution that makes, and NaOH content is 5～12wt%; Urea content is no more than 18wt%, and all the other are water.
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| CN201110273050.3A CN102432891B (en) | 2011-09-15 | 2011-09-15 | Method for dissolving cellulose |
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| CN201110273050.3A CN102432891B (en) | 2011-09-15 | 2011-09-15 | Method for dissolving cellulose |
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| CN102432891B CN102432891B (en) | 2014-02-12 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105542194A (en) * | 2016-03-09 | 2016-05-04 | 天津商业大学 | Sodium hydroxide/sodium cyclamate aqueous solvent system for dissolving pulp cellulose |
| CN105694064A (en) * | 2016-03-09 | 2016-06-22 | 天津商业大学 | Sodium hydroxide/sodium sulfamate aqueous solvent system for dissolving pulp cellulose |
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| JPS6042401A (en) * | 1983-08-17 | 1985-03-06 | Asahi Chem Ind Co Ltd | Alkali-soluble cellulose |
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| CN101037479A (en) * | 2007-04-13 | 2007-09-19 | 武汉大学 | Method for dissolving cellulos |
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| CN101275369A (en) * | 2007-03-26 | 2008-10-01 | 江苏龙马绿色纤维有限公司 | Cellulose-dissolved dissolvant and industrial method thereof |
| CN101412813A (en) * | 2008-05-26 | 2009-04-22 | 东华大学 | Cellulose solution prepared with low energy consumption and novel preparation thereof |
| CN101412815A (en) * | 2008-05-26 | 2009-04-22 | 东华大学 | Novel cellulose solution and preparation thereof |
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2011
- 2011-09-15 CN CN201110273050.3A patent/CN102432891B/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6042401A (en) * | 1983-08-17 | 1985-03-06 | Asahi Chem Ind Co Ltd | Alkali-soluble cellulose |
| CN1482159A (en) * | 2003-07-25 | 2004-03-17 | 武汉大学 | Solvent composite and preparation method and use thereof |
| CN101275369A (en) * | 2007-03-26 | 2008-10-01 | 江苏龙马绿色纤维有限公司 | Cellulose-dissolved dissolvant and industrial method thereof |
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| CN101074285A (en) * | 2007-06-22 | 2007-11-21 | 武汉大学 | Method for dissolving cellulose |
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| CN101412813A (en) * | 2008-05-26 | 2009-04-22 | 东华大学 | Cellulose solution prepared with low energy consumption and novel preparation thereof |
| CN101412815A (en) * | 2008-05-26 | 2009-04-22 | 东华大学 | Novel cellulose solution and preparation thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105542194A (en) * | 2016-03-09 | 2016-05-04 | 天津商业大学 | Sodium hydroxide/sodium cyclamate aqueous solvent system for dissolving pulp cellulose |
| CN105694064A (en) * | 2016-03-09 | 2016-06-22 | 天津商业大学 | Sodium hydroxide/sodium sulfamate aqueous solvent system for dissolving pulp cellulose |
| CN105542194B (en) * | 2016-03-09 | 2017-11-21 | 天津商业大学 | Dissolve sodium hydroxide/sodium cyclohexylsulfamate aqueous solvent system of pulp cellulose |
| CN105694064B (en) * | 2016-03-09 | 2017-11-21 | 天津商业大学 | Dissolve sodium hydroxide/sulfamic acid sodium water solution dicyandiamide solution of pulp cellulose |
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