CN102432891B - Method for dissolving cellulose - Google Patents
Method for dissolving cellulose Download PDFInfo
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- CN102432891B CN102432891B CN201110273050.3A CN201110273050A CN102432891B CN 102432891 B CN102432891 B CN 102432891B CN 201110273050 A CN201110273050 A CN 201110273050A CN 102432891 B CN102432891 B CN 102432891B
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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 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 environment-friendly polymers, and is expected one of main industrial chemicals becoming 21 century.Mierocrystalline cellulose can be widely used in the technical fields such as weaving, papermaking, tobacco, food, agricultural and petrochemical complex.The whole world, for the Mierocrystalline cellulose of the papermaking of weaving, just reaches 8,000,000 tons every year.But current more than 90% regenerated cellulose product still adopts traditional viscose process to produce, as J.Macromol.Sci.-Rev.Macromol.Chem., 1980, C18 (1), the method adopting in 1 is, Mierocrystalline cellulose under highly basic effect with CS
2reaction generates cellulose xanthate, after be dissolved in dilute alkaline soln Making viscose liquid.Mierocrystalline cellulose viscose is regenerated after spray silk or curtain coating in dilute acid soln, makes viscose fiber or glassine paper.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.With cuprammonium process, producing cuprammonium regenerated fiber 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), (U.S.Patent 4302252 for LiCl/DMAc, 1981) industrialization that etc., so far there are no for various reasons.N-methyl morpholine oxide (MMNO) (J.Polym.Sci.:Polym.Lett.Ed.1979,17,219) was once acknowledged as the most promising cellosolve.1978, first German Akzo Nobel company obtained its cellulosic fibre solvent-spinning method patent, and obtained production technique patent in 1980.The international artificial silk in Brussels in 1989 and the synthon Bureau of Standards (BISFA) are " Lyocell " the category name of the cellulosic fibre of being manufactured by these class methods.After this, a small amount of cellulosic fibrous product of preparing with it in the world comes into the market, but because solvent is expensive, spinning temperature is higher, suitability for industrialized production slower development.In addition, reported that Mierocrystalline cellulose and urea at high temperature react generation cellulose carbamate, be then directly dissolved in and in sig water, obtain spinning solution (Finnish Patent 61003; 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 by cellulose dissolution in the solvent being chilled in advance, this method used time is short, and efficiency is high, pollution-free and cheap, nontoxic and recyclable the recycling of solvent used, therefore be a kind of green production process, but the method energy loss-rate is large, need to be at precooling 1 ton of solvent nearly as dissolved 42 kilograms of Mierocrystalline celluloses, not only bad for energy-saving consumption-reducing, and be difficult to industrialized production.The people such as Kamide have reported that Mierocrystalline cellulose is at 2.5molL
-1dissolving in the NaOH aqueous solution, but this solvent must be used the polymerization degree lower than 250 the wood pulp cellulose of processing through steam explosion, and it is dissolvable in water (Japan Patent1777283,1983 in NaOH solution when 4 ℃ of left and right; U.S.Patent 4634470:Polymer J., 1984,12,857; Polymer J., 1988,20,447), and obtained fiber yarn intensity is extremely low.Chinese patent 00114486.3 discloses a kind of solvent compositions of dissolving cellulos for cellulosic dissolving, and this solvent compositions can only dissolve the Mierocrystalline cellulose of molecular weight (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 object of the invention is to overcome the problem existing in above-mentioned existing cellulose dissolution method, provide that a kind of dissolving cellulos efficiency is high, method environmental protection, energy-saving consumption-reducing and be easy to realize the method for industrialized production.
Realize the technical scheme that the object of the invention adopts as follows:
A kind of method of dissolving cellulos, take wood pulps, Cotton Pulp, hemp dissolving pulp, bamboo pulp, bagasse pulp, straw fiber slurry, cellulosic nonwoven fabric or steam in quick-fried cellulose slurry at least one be cellulosic material, cellulosic material, NaOH and water are stirred and make transparent cellulose solution at-15-50 ℃, in the cellulose solution making, content of cellulose is 2-8wt%, NaOH content is 5～12wt%, and all the other are water.
Or by cellulosic material, NaOH, water, and urea stirs at-15-50 ℃, makes transparent cellulose solution, in the cellulose solution making, content of cellulose is 2-8wt%, NaOH content is 5～12wt%, and urea content is no more than 18wt%, and all the other are water.
Or first cellulosic material is dispersed in the urea soln that concentration is no more than 18wt%, at-15-50 ℃, stir, then adding NaOH or concentration is 6-12wt%NaOH solution, continuation stirs and makes transparent cellulose solution at-15-50 ℃, in the cellulose solution making, content of cellulose is 2-8wt%, NaOH content is 5～12wt%, and urea content is no more than 18wt%, and all the other are water.
Or first NaOH and water are made to the NaOH solution that concentration is 6-12wt%, cellulosic material is dispersed in NaOH solution again, at-15-50 ℃, stirs and make cellulose solution, in the cellulose solution making, content of cellulose is 2-8wt%, NaOH content is 5～12wt%, and all the other are water.
Or first cellulosic material is dispersed in the NaOH solution that concentration is 6-12wt%, at-15-50 ℃, stir, then add urea or concentration to be no more than the urea soln of 18wt%, continuation stirs and makes transparent cellulose solution at-15-50 ℃, in the cellulose solution making, content of cellulose is 2-8wt%, NaOH content is 5～12wt%, and urea content is no more than 18wt%, and all the other are water.
As shown from the above technical solution, the present invention is in fact that employing NaOH solution is solvent, or take NaOH solution as main solvent, urea soln is secondary solvent, by the amount ratio between strict control solute Mierocrystalline cellulose and solvent, thereby make cellulosic material under room temperature, directly be dissolved in fast the Mierocrystalline cellulose strong solution that makes high-dissolvability in solvent.The method is usingd low-cost sodium hydroxide and urea soln as solvent, and directly solvent polymerization degree is up to 550 Mierocrystalline cellulose.
The present invention can be used for industrial dissolving cellulos, for papermaking or prepare various cellulose silks, film, non-woven fabrics and chromatographic column protruded packing.Also can be used on 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, advantage of the present invention is as follows:
The present invention adopts sodium hydroxide solution or sodium hydroxide and urea mixing solutions as solvent direct fast dissolving cellulos at room temperature.In dissolution process, temperature is-normal room temperature of 15-50 ℃, without pre-cold solvent, has obviously reduced energy consumption.In final solution, the concentration of sodium hydroxide, urea is respectively 5-12wt% and is no more than 18wt%, and concentration range is also within reason narrow, easily meets industrial requirements.And as long as can reaching 100%, 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 dissolves completely, can make the strong solution of higher molecular weight (mean polymerisation degree up to 550 Mierocrystalline cellulose), and dissolution rate is very fast, soon several minutes, in several hours, can fully dissolve slowly.Method provided by the invention can be used the common equipment of traditional adhering process to complete, 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 in method provided by the invention, related dissolving and regeneration is all physical process, and any chemical reaction does not occur, the easy recycling use of solvent, 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 of the present invention is high, method environmental protection, energy-saving consumption-reducing and be easy to realize the method for industrialized production.
Embodiment
Below in conjunction with specific embodiment, technical scheme of the present invention is described further:
Embodiment 1
At 45 ℃ of room temperatures, by the Cotton Pulp of 5g or bamboo pulp, bagasse pulp, straw fiber slurry, cellulosic nonwoven fabric or steam in the 8wt%NaOH solution of a kind of 90g of joining in quick-fried cellulose slurry and fully stir 2 hours rapidly, add wherein again 5g urea, at 45 ℃, stir half an hour, can obtain cellulose solution.In the cellulose solution making, content of cellulose is 5wt%, and NaOH content is about 7.2wt%, and urea content is 5wt%, and all the other are water.
Embodiment 2
At 20 ℃ of room temperatures, by the wood pulps of 6g, Cotton Pulp, hemp dissolving pulp, bamboo pulp, bagasse pulp, straw fiber slurry, cellulosic nonwoven fabric or steam in the 12wt%NaOH solution of a kind of 80g of joining in quick-fried cellulose slurry and fully stir 1 hour rapidly, add wherein again 14g urea, at 20 ℃, stir one hour, can obtain cellulose solution.In the cellulose solution making, content of cellulose is 6wt%, and NaOH content is about 9.6wt%, and urea content is about 14wt%, and all the other are water.
Embodiment 3
At 15 ℃ of room temperatures, the hemp dissolving pulp of 2g is joined in the 10wt%NaOH solution of 58g and stir 0.5 hour rapidly, then add wherein the 18wt% urea of 40g, at 15 ℃, stir one hour, can obtain transparent cellulose solution.In the cellulose solution making, content of cellulose is 2wt%, and NaOH content is about 5.8wt%, and urea content is about 7.2wt%, and all the other are water.
Embodiment 4
At 4 ℃ of room temperatures, using the wood pulps of 8g, Cotton Pulp, hemp dissolving pulp, bamboo pulp, bagasse pulp, straw fiber slurry, cellulosic nonwoven fabric or steam one or more in quick-fried cellulose slurry and join in the 12wt%NaOH solution of 80g and stir 2 hours rapidly as raw material, add wherein again 12g urea, at 4 ℃, stir one hour, can obtain vitreous fibre cellulose solution.In the cellulose solution making, content of cellulose is 8wt%, and NaOH content is 9.6wt%, and urea content is 7.2wt%, and all the other are water.
Embodiment 5
At 25 ℃ of room temperatures, the bamboo pulp of 6g and 8g NaOH are mixed, add 74mL water, stir half an hour rapidly, then add wherein 12g urea, at 25 ℃, stir one hour, can obtain transparent cellulose solution.In the cellulose solution making, content of cellulose is 6wt%, and NaOH content is about 8wt%, and urea content is about 12wt%, and all the other are water.
Embodiment 6
At 5 ℃ of room temperatures, the Cotton Pulp of 6g and 12g urea are mixed, add 74mL water, stir half an hour rapidly, then add 8gNaOH wherein, at 5 ℃, stir one hour, can obtain transparent cellulose solution.In the cellulose solution making, content of cellulose is 6wt%, and NaOH content is about 8wt%, and urea content is about 12wt%, and all the other are water.
Embodiment 7
At 5 ℃ of room temperatures, the Cotton Pulp of 5g and 8g NaOH are mixed, add 87mL water, stir rapidly one hour, can obtain cellulose solution.In the cellulose solution making, content of cellulose is 5wt%, and NaOH content is about 8wt%, and all the other are water.
Embodiment 8
At 25 ℃ of room temperatures, by the wood pulps of 5g, Cotton Pulp, hemp dissolving pulp, bamboo pulp, bagasse pulp, straw fiber slurry, cellulosic nonwoven fabric or steam in the 8wt%NaOH solution of a kind of 95g of adding in quick-fried cellulose slurry, stir one hour rapidly, can obtain cellulose solution.In the cellulose solution making, content of cellulose is 5wt%, and NaOH content is about 7.6wt%, and all the other are water.
Above-described embodiment all can carry out at-15 ℃-0 ℃.
Claims (4)
1. a cellulosic dissolving method, it is characterized in that: take wood pulps, Cotton Pulp, hemp dissolving pulp, bamboo pulp, bagasse pulp, straw fiber slurry, cellulosic nonwoven fabric or steam in quick-fried cellulose slurry at least one be cellulosic material, cellulosic material, NaOH and water are stirred and makes transparent cellulose solution at 5-50 ℃, in the cellulose solution making, content of cellulose is 2-8wt%, NaOH content is 5 ~ 12wt%, and all the other are water.
2. cellulosic dissolving method according to claim 1, it is characterized in that: first NaOH and water are made to the NaOH solution that concentration is 6-12wt%, cellulosic material is dispersed in NaOH solution again, at 5-50 ℃, stir and make cellulose solution, in the cellulose solution making, content of cellulose is 2-8wt%, NaOH content is 5 ~ 12wt%, and all the other are water.
3. cellulosic dissolving method according to claim 1, it is characterized in that: by cellulosic material, NaOH, water, and urea stirs at 5-50 ℃, make transparent cellulose solution, in the cellulose solution making, content of cellulose is 2-8wt%, NaOH content is 5 ~ 12wt%, and urea content is no more than 18wt%, and all the other are water.
4. cellulosic dissolving method according to claim 2, it is characterized in that: first cellulosic material is dispersed in the urea soln that concentration is no more than 18wt%, at 5-50 ℃, stir, then adding NaOH or concentration is 6-12wt% NaOH solution, continuation stirs and makes transparent cellulose solution at 5-50 ℃, and in the cellulose solution making, content of cellulose is 2-8wt%, 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 true CN102432891B (en) | 2014-02-12 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1482159A (en) * | 2003-07-25 | 2004-03-17 | 武汉大学 | Solvent composite and preparation method and use thereof |
| CN101037479A (en) * | 2007-04-13 | 2007-09-19 | 武汉大学 | Method for dissolving cellulos |
| CN101074285A (en) * | 2007-06-22 | 2007-11-21 | 武汉大学 | Method for dissolving cellulose |
| CN101130605A (en) * | 2007-10-16 | 2008-02-27 | 武汉大学 | Solvent composition for solubilizing cellulose |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6042401A (en) * | 1983-08-17 | 1985-03-06 | Asahi Chem Ind Co Ltd | Alkali-soluble cellulose |
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101037479A (en) * | 2007-04-13 | 2007-09-19 | 武汉大学 | Method for dissolving cellulos |
| CN101074285A (en) * | 2007-06-22 | 2007-11-21 | 武汉大学 | Method for dissolving cellulose |
| CN101130605A (en) * | 2007-10-16 | 2008-02-27 | 武汉大学 | Solvent composition for solubilizing cellulose |
| 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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