CN102443869A - Cellulose solution coagulation forming method - Google Patents
Cellulose solution coagulation forming method Download PDFInfo
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- CN102443869A CN102443869A CN2011102843643A CN201110284364A CN102443869A CN 102443869 A CN102443869 A CN 102443869A CN 2011102843643 A CN2011102843643 A CN 2011102843643A CN 201110284364 A CN201110284364 A CN 201110284364A CN 102443869 A CN102443869 A CN 102443869A
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Abstract
The invention discloses a cellulose solution coagulation forming method, which comprises the following steps of: (1) dissolving cellulose pulp into a mixed aqueous solution consisting of urea or thiourea, alkali metal hydroxide and water to obtain a cellulose solution; (2) curing the cellulose solution in the (1) in a non-acid first coagulation bath at the temperature of between 50 and 100 DEG C, wherein the concentrations of the urea/ thiourea and the alkali metal hydroxide are lower than those of the corresponding components in the (1); and (3) obtaining cellulose fibers by subsequent treatment. The product has drawing plasticity, and can create an advantage for improving the strength. The production process and the production equipment of the forming method are simple, the equipment and the plant are not corroded in the production process, and the production costs of urea solvent cellulose fibers, glass paper, films, sponge and related products generated by the cellulose solution are greatly reduced; and the method has high economic benefit and social environment-friendly benefit.
Description
Technical field
The present invention relates to a kind of method of cellulose solution solidification forming, particularly the manufacturing process of urea solvent method fiber cellulose solution.
Background technology
Cellulose is the abundantest renewable polymer that nature exists; Have good biocompatibility, many good performances such as biological degradability can be used for preparing the plain product of multiple functional fibre; Wherein, Aqueous slkali is current extremely promising cellulose solvent system, NaOH/urea etc. for example, cellulose solution moulding in acid coagulating bath afterwards.For example one Chinese patent application numbers 200710021068.8 discloses the commercial run of preparation regenerated cellulose fiber; With cellulose dissolution in solvent; Fully stir, make cellulose solution; With cellulose solution through filtration, deaeration, spray silk, coagulating bath solidify, washing, drawing-off, oven dry make regenerated cellulose fiber, wherein coagulating bath is that sulfuric acid and aqueous sodium persulfate solution are arranged.One Chinese patent application 200410013389.X discloses a kind of preparation method of regenerated celulose fibre; With cellulose dissolution in 5-12wt% NaOH and 8-20wt% urea mixed aqueous solution; Fully stir; Make the cellulose concentrated solution; Adopt wet spinning process to solidify spraying silk on the spinning machine and in coagulating bath, regenerate, said coagulating bath is 3-25wt% aqueous sulfuric acid, 3-25wt% sulfuric acid/5-30wt% aqueous sodium persulfate solution, 3-25wt% sulfuric acid/5-30wt% ammonium sulfate solution etc.And in the method for one Chinese patent application number 200510018799.8 disclosed preparing regenerative cellulose fiber by two-step coagulating bath process, coagulating bath consist of 5-20wt% sulfuric acid/10-25wt% sodium sulphate mixed aqueous solution.
Above-mentioned cellulose solution all adopts the chemical reaction moulding, and its forming speed is fast, but has consumed raw material sulfuric acid and NaOH, and has produced cheap not tractable sodium sulfate byproduct.The hydrogeneous sodium oxide molybdena amount of urea solvent method fiber cellulose solution is bigger; If the method that does not adopt physics to be shaped; Just must cause a large amount of consumption of raw material such as urea, NaOH, sulfuric acid with said method, produce a large amount of sodium sulfate byproduct, make that also the recovery of urea is very difficult; Caused the product cost of this production technology very high, in addition environment has been affected.Aspect quality; Test once uses sulfuric acid reaction to make the fiber of fibre forming have certain fragility and intensity very low; Possibly be to cause that the structure of fibrous inside and appearance is inhomogeneous because the alkali of a large amount of acid and cellulose solution plays violent exothermic reaction, what make that the cellulose solution of the degree of polymerization very high (DP=500～600) obtains but is the very low fiber of intensity.
Given this, special proposition the present invention.
Summary of the invention
The purpose of this invention is to provide the method that a kind of cellulose fibre solution solidifies is shaped; First coagulating bath of this method is nonacid coagulating bath; The solvent of first coagulating bath can recycle and reuse, and the consumption of having practiced thrift bronsted lowry acids and bases bronsted lowry has also reduced the recovery to sulfate simultaneously; And the fiber that obtains has more pliability.
For realizing goal of the invention of the present invention, a kind of method of cellulose solution solidification forming comprises the steps:
(1) cellulose pulp is dissolved in the mixed aqueous solution of urea or thiocarbamide, alkali metal hydroxide and water composition, obtains cellulose solution;
(2) cellulose solution that obtains of step (1) solidifies in first coagulating bath; The composition of described first coagulating bath comprises the mixed aqueous solution that urea/sulphur urea, alkali metal hydroxide and water are formed; Temperature is 50～100 ℃; Wherein, the concentration of urea/sulphur urea and alkali metal hydroxide all is lower than the corresponding used concentration of component of step (1), does not have the adding of acidic materials in first coagulating bath;
(3) the solid-state fiber behind final the curing carries out drawing-off, cut-out, refining, oven dry, packing process and obtains cellulose fibre.
The component that coagulating bath is adopted in step (2) is pure water or NaOH and thiocarbamide/urea; But its concentration will be lower than the concentration of step (1) respective components; Because the high concentration material can be free to low concentration side's diffusion principle; Solidify water temperature, coagulating bath amount, coagulation bath composition through adjusting; Alkali and the urea speed that (the low concentration aqueous solution here is with respect to alkali in the cellulose solution and urea concentration) freely diffuses out among (alkali-free and urea) or the low concentration aqueous solution in water in can the controlling fiber cellulose solution; And the stabilising system of urea method cellulose solution becomes unstable owing to the spread apart of alkali and urea, to reach the solidification forming purpose; And coagulation bath temperature is controlled in 50～100 ℃ the scope; (described solute molecule is the cellulose macromolecule not can to improve solute molecule in the cellulose solution in this temperature; It mainly is the micromolecule diffusion; Because micromolecule diffusion motion speed is fast) speed (speed that causes cellulose solution to be shaped) that spreads in the coagulating bath, can be unlikely to again urea is decomposed fast.In first coagulating bath, there is not acid to participate in carrying out chemical reaction, can not produce and reclaim complicacy and the cheap sodium sulfate byproduct in market.
The mass percent concentration of urea/sulphur urea is 0～1% in the middle coagulating bath of step (2), preferred 0.4%.
The mass percent concentration of alkali metal hydroxide is 0～1% in the middle coagulating bath of step (2), preferred 0.3%.
Preferably, in the step (1), the mass percent concentration of alkali metal hydroxide is 5～10%, and the mass percent concentration of urea/sulphur urea is 6～13%.
Preferably, in the step (2), the concentration 0～1% of alkali metal hydroxide, the mass percent concentration of urea or thiocarbamide is 0～1%.
In the method for the present invention, the component of first coagulating bath is different with the disclosed coagulating bath of prior art, and the component of first coagulating bath of the present invention does not contain acid.In the fibre forming process, according to actual needs, can only use the present invention's first coagulating bath, also can the present invention's first coagulating bath be used in combination with the coagulating bath of prior art and prepare required fiber.
The shaping of cellulose solution is very slow with respect to spinning speed, so just must increase the length of bath-fed tube, bath-fed tube length is long more; Tow is long more in the coagulating bath time of staying, and urea that diffuses out and alkali are many more, and fibre forming is finer and close; Fibre strength is big more, and forming effect is good more.
The coagulating tank of the present invention's first coagulating bath can be slot type or bobbin formula, and coagulating bath groove depth or coagulating bath bobbin length are 600～1500mm, preferred 1000～1200mm.
In first coagulating bath among the present invention, the coagulating bath flow is 20 times greater than the cellulose solution volume flow; Preferred 30-40 doubly.
Preferably, in the described method, between step (2), (3), also further comprise the steps:
(a) the solid-state fiber after step (2) is solidified is through solidifying wherein in second coagulating bath after the drawing-off, and the inorganic acid that consists of 1～10wt% concentration of described second coagulating bath, coagulation bath temperature are 60～100 ℃, and preferred, described inorganic acid is a sulfuric acid.
That is: said method is:
(1) cellulose pulp is dissolved in the mixed aqueous solution of urea or thiocarbamide, alkali metal hydroxide and water composition, obtains cellulose solution;
(2) cellulose solution that obtains of step (1) solidifies in first coagulating bath; The composition of described first coagulating bath comprises the mixed aqueous solution that urea/sulphur urea, alkali metal hydroxide and water are formed; Temperature is 50～100 ℃; Wherein, the concentration of urea/sulphur urea and alkali metal hydroxide all is lower than the corresponding used concentration of component of step (1);
(3) the solid-state fiber after step (2) is solidified is through solidifying wherein in second coagulating bath after the drawing-off, and the inorganic acid that consists of 1～10wt% concentration of described second coagulating bath, coagulation bath temperature are 60～100 ℃, and preferred, described inorganic acid is a sulfuric acid,
Solid-state fiber after second coagulating bath is solidified carries out drawing-off, cut-out, refining, oven dry, packing process again and obtains cellulose fibre.
Preferably, in the described method, between step (2), (3), also further comprise the steps
(a) the solid-state fiber after step (2) is solidified is through solidifying in second coagulating bath after the drawing-off, and wherein, the inorganic acid that consists of 1～10wt% concentration of described second coagulating bath, coagulation bath temperature are 60～100 ℃, and preferred, described inorganic acid is a sulfuric acid;
(b) the solid-state fiber after step (a) is solidified needs a drawing-off at least, and solid-state fiber carries out drawing-off in the 3rd coagulating bath, and wherein, described the 3rd coagulating bath is that temperature is 60～100 ℃ water or a water vapour, and it is preferred, and temperature is 95 ℃ a water.
That is: said method is:
(1) cellulose pulp is dissolved in the mixed aqueous solution of urea or thiocarbamide, alkali metal hydroxide and water composition, obtains cellulose solution;
(2) cellulose solution that obtains of step (1) solidifies in first coagulating bath; The composition of described first coagulating bath comprises the mixed aqueous solution that urea/sulphur urea, alkali metal hydroxide and water are formed; Temperature is 50～100 ℃; Wherein, the concentration of urea/sulphur urea and alkali metal hydroxide all is lower than the corresponding used concentration of component of step (1);
(3) the solid-state fiber after step (2) is solidified is through solidifying in second coagulating bath after the drawing-off, and wherein, the inorganic acid that consists of 1～10wt% concentration of described second coagulating bath, coagulation bath temperature are 60～100 ℃, and preferred, described inorganic acid is a sulfuric acid;
(4) the solid-state fiber after step (3) is solidified needs a drawing-off at least, and solid-state fiber carries out drawing-off in the 3rd coagulating bath, and wherein, described the 3rd coagulating bath is that temperature is 60～100 ℃ water or a water vapour, and it is preferred, and temperature is 95 ℃ a water;
Fiber after the 3rd coagulating bath is solidified carries out drawing-off, cut-out, refining, oven dry, packing process again and obtains cellulose fibre.
Comprise further also in first coagulating bath that trace solidifies auxiliary agent, for example AC1815 etc.
In first coagulating bath, the tow traffic direction is consistent with the body lotion flow direction.
In second and third coagulating bath, the tow traffic direction is consistent with the body lotion flow direction.
The above-mentioned method of operation can reduce the frictional force of fiber and coagulating bath, improves the fibre forming effect.Water is mobile in the bobbin, both can make fibre forming complete, can take fibre bundle out of bobbin again, makes simple to operate.
Spinning bath curring time (the first coagulating bath time of staying) is 0～10s.
Use the 3rd coagulating bath serviceability temperature be 60-100 ℃ water (also can add a small amount of various auxiliary agent that function is used that improves) as coagulating agent, simply make the specific urea cellulose made by soloent process solution solidifies of quality index become various forms of products smoothly.
In the method for fiber solution solidification forming of the present invention, coagulating bath does not have corrosiveness to spinning head and other assembly, like this filament spinning component material is required and can reduce, thereby can reduce cost, prolongs spinning head service life.After making fibre forming, do not rupture,, carry out-15～0% negative drawing-off from the tow that spinning head comes out; 5%～30% positive drawing-off is adopted in the second coagulating bath drawing-off; 5%～30% positive drawing-off is adopted in the 3rd coagulating bath drawing-off.
Use acid solution that fibrous inside alkali thoroughly is neutralized in second coagulating bath and urea is all decomposed or washes out, thereby reach complete solidification forming purpose.Through the plasticizing drawing-off of the 3rd coagulating tank, the plasticity of gained fiber improves, and can improve drafting multiple, reduces fiber weakness, and fiber product is done by force and is significantly improved by force with wet.
The beneficial effect that the present invention gives prominence to is following:
The method of cellulose solution solidification forming of the present invention through the double diffusion principle of physics, is sought best forming temperature, and it is rapid, even, stable that cellulose solution is shaped.And traditional viscose production technology and former urea method cellulose solution are shaped chemical substances such as being to use sulfuric acid as coagulating bath; Make cellulose solution generate cellulose fibre through chemical reaction; Chemical reaction process has consumed NaOH and sulfuric acid; Produce cheap accessory substances such as a large amount of sodium sulphate, made solvent be difficult to reclaim, increased the cost of coagulating bath recycling and the complexity of production technology greatly.The consumption of NaOH is 520Kg/ ton fiber in traditional viscose production, and sulfuric acid is 720Kg/ ton fiber.Especially with the Related product project of urea solvent method fiber cellulose solution; Calculate (the coagulating bath method that sulfuric acid is arranged) by the production method that sulfuric acid neutralization reaction solidification forming is arranged; 1.7 tons in product fiber consumption sulfuric acid per ton, 1.4 tons in consumption NaOH is also having very large difficulty aspect the urea solvent recovery.Coagulating bath behind the method solidification forming of the present invention can be carried out purifying, enrichment, recycle through the method that films such as simple counter-infiltration, sodium filter separate; Almost not loss of solvent in its process; Meet the requirement of cleaner production and environmental protection protection; And the plasticity of gained fiber improves, and can improve drafting multiple, and fiber product is done strong and wet and is significantly improved by force.
The specific embodiment
Below to combining the specific embodiment to further detailed introduction of technical scheme of the present invention.
Embodiment 1
Cellulose pulp is dissolved in the mixed aqueous solution of urea, NaOH and water composition; Obtain cellulose solution; The mass percent concentration of pulp is 4.96%, and the mass percent concentration of urea is 11.45%, and the mass percent concentration of NaOH is 6.61%; The cellulose solution that obtains solidifies in first coagulating bath, and first coagulating bath is that temperature is 95 ℃ a pure hot water, and other consists of zero.First coagulating bath is solidified cellulose solution and is used directly discharging of back, does not recycle; After getting into the godet roller drawing-off, solid-state fiber after spinning machine spinning head place coagulating tank solidifies for the first time in second coagulating bath, solidifies again; Obtain cellulose fibre through follow-up processing again; Wherein, the sulfuric acid that consists of 5wt% concentration of second coagulating bath, coagulation bath temperature are 90 ℃; Fiber gets into the 3rd coagulating bath then, and the 3rd coagulating bath is 62 ℃ high-temperature-hot-water for the bath temperature.The over dry intensity of the cellulose fibre that obtains: 1.62cN/dtex.
Embodiment 2
Cellulose pulp is dissolved in the mixed aqueous solution of urea, NaOH and water composition; Obtain cellulose solution; The mass percent concentration of pulp is 4.87%, and the mass percent concentration of urea is 11.69%, and the mass percent concentration of NaOH is 6.90%; The cellulose solution that obtains solidifies in first coagulating bath; The temperature of first coagulating bath is 90 ℃; It is 900mm that tube length degree (the dipping bath degree of depth) is bathed in first coagulating bath; The coagulating bath flow is 35 times of cellulose solution volume flow, and the mass percent concentration of urea wherein is 0.3%, and the mass percent concentration of NaOH is 0.1%; After getting into the godet roller drawing-off, solid-state fiber after spinning machine spinning head place coagulating tank solidifies for the first time in second coagulating bath, solidifies again; Obtain cellulose fibre through follow-up processing again; Wherein, the sulfuric acid that consists of 2wt% concentration of second coagulating bath, coagulation bath temperature are 98 ℃; Fiber gets into the 3rd coagulating bath then, and the 3rd coagulating bath is 80 ℃ hot water for the bath temperature.The over dry intensity of the cellulose fibre that obtains: 1.65cN/dtex.
Embodiment 3
Cellulose pulp is dissolved in the mixed aqueous solution of urea, NaOH and water composition; Obtain cellulose solution; The mass percent concentration of pulp is 5.03%, and the mass percent concentration of urea is 11.90%, and the mass percent concentration of NaOH is 7.10%; The cellulose solution that obtains solidifies in first coagulating bath; The temperature of first coagulating bath is 65 ℃; It is 700mm that tube length degree (the dipping bath degree of depth) is bathed in first coagulating bath; The coagulating bath flow is 40 times of cellulose solution volume flow, and the mass percent concentration of urea is 0.2% in the coagulation bath composition, and the mass percent concentration of NaOH is 0.1%; After getting into the godet roller drawing-off, solid-state fiber after spinning machine spinning head place coagulating tank solidifies for the first time in second coagulating bath, solidifies again; Obtain cellulose fibre through follow-up processing again; Wherein, the sulfuric acid that consists of 10wt% concentration of second coagulating bath, coagulation bath temperature are 63 ℃; Fiber gets into the 3rd coagulating bath then, and the 3rd coagulating bath is 61 ℃ hot water for the bath temperature.The over dry intensity of the cellulose fibre that obtains: 1.65cN/dtex.
Embodiment 4
Cellulose pulp is dissolved in the mixed aqueous solution of urea, NaOH and water composition; Obtain cellulose solution; The mass percent concentration of pulp is 4.86%, and the mass percent concentration of urea is 11.93%, and the mass percent concentration of NaOH is 7.23%; The cellulose solution that obtains solidifies in first coagulating bath.The temperature of first coagulating bath is 95 ℃, and the mass percent concentration of urea is 0.9% in the coagulating bath, and the mass percent concentration of NaOH is 0.4%; After getting into the godet roller drawing-off, solid-state fiber after spinning machine spinning head place coagulating tank solidifies for the first time in second coagulating bath, solidifies again; Obtain cellulose fibre through follow-up processing again; Wherein, the sulfuric acid that consists of 3wt% concentration of second coagulating bath, coagulation bath temperature are 90 ℃.Fiber gets into the 3rd coagulating bath then, and the 3rd coagulating bath is that the bath temperature is 90 ℃ a hot water, the over dry intensity of the cellulose fibre that obtains: 1.61cN/dtex.
Embodiment 5
Cellulose pulp is dissolved in the mixed aqueous solution of urea, NaOH and water composition; Obtain cellulose solution; The mass percent concentration of pulp is 4.92%, and the mass percent concentration of urea is 11.65%, and the mass percent concentration of NaOH is 7.20%; The cellulose solution that obtains solidifies in first coagulating bath; The temperature of first coagulating bath is 97 ℃; It is 900mm that tube length degree (the dipping bath degree of depth) is bathed in first coagulating bath, and the coagulating bath flow is 30 times of cellulose solution volume flow, wherein; The mass percent concentration of urea is 0.4%, and the mass percent concentration of NaOH is 0.2%; After getting into the godet roller drawing-off, solid-state fiber after spinning machine spinning head place coagulating tank solidifies for the first time in second coagulating bath, solidifies again; Obtain cellulose fibre through follow-up processing again; Wherein, the sulfuric acid that consists of 6wt% concentration of second coagulating bath, coagulation bath temperature are 96 ℃.Fiber gets into the 3rd coagulating bath then, and the 3rd coagulating bath is that the bath temperature is 65 ℃ a hot water, the over dry intensity of the cellulose fibre that obtains: 1.69cN/dtex.
Embodiment 6
Cellulose pulp is dissolved in the mixed aqueous solution of urea, NaOH and water composition; Obtain cellulose solution; The mass percent concentration of pulp is 4.72%, and the mass percent concentration of urea is 6.22%, and the mass percent concentration of NaOH is 10.00%; The cellulose solution that obtains solidifies in first coagulating bath, and the coagulation bath temperature of first coagulating bath is 50 ℃, and wherein, the mass percent concentration of urea is 0.3%, and the mass percent concentration of NaOH is 1.0%; After getting into the godet roller drawing-off, solid-state fiber after spinning machine spinning head place coagulating tank solidifies for the first time in second coagulating bath, solidifies again; Obtain cellulose fibre through follow-up processing again; Wherein, the sulfuric acid that consists of 6wt% concentration of second coagulating bath, coagulation bath temperature are 96 ℃.The over dry intensity of the cellulose fibre that obtains: 1.57cN/dtex.
Embodiment 7
Cellulose pulp is dissolved in the mixed aqueous solution of urea, NaOH and water composition; Obtain cellulose solution; The mass percent concentration of pulp is 5.22%, and the mass percent concentration of urea is 13.0%, and the mass percent concentration of NaOH is 6.0%; The cellulose solution that obtains solidifies in first coagulating bath; The coagulation bath temperature of first coagulating bath is 80 ℃, and wherein, the mass percent concentration of urea is 0.3%; The mass percent concentration of NaOH is 1.0%, advances drawing-off, cut-out, refining, oven dry, packing again and obtains cellulose fibre.The over dry intensity of the cellulose fibre that obtains: 1.52cN/dtex.
Embodiment 8
Cellulose pulp is dissolved in the mixed aqueous solution of urea, NaOH and water composition; Obtain cellulose solution; The mass percent concentration of pulp is 4.90%, and the mass percent concentration of urea is 11.50%, and the mass percent concentration of NaOH is 6.62%; The cellulose solution that obtains solidifies in first coagulating bath, and it is 1200mm that tube length degree (the dipping bath degree of depth) is bathed in first coagulating bath, and temperature is 95 ℃ a pure hot water, and other consists of zero, and the coagulating bath flow is 40 times of cellulose solution volume flow.First coagulating bath is solidified cellulose solution and is used directly discharging of back, does not recycle; After getting into the godet roller drawing-off, solid-state fiber after spinning machine spinning head place coagulating tank solidifies for the first time in second coagulating bath, solidifies again; Obtain cellulose fibre through follow-up processing again; Wherein, the sulfuric acid that consists of 5wt% concentration of second coagulating bath, coagulation bath temperature are 90 ℃; Fiber gets into the 3rd coagulating bath then, and the 3rd coagulating bath is 62 ℃ high-temperature-hot-water for the bath temperature.The over dry intensity of the cellulose fibre that obtains: 1.70cN/dtex.
Embodiment 9
Cellulose pulp is dissolved in the mixed aqueous solution of urea, NaOH and water composition; Obtain cellulose solution; The mass percent concentration of pulp is 4.70%, and the mass percent concentration of urea is 6.81%, and the mass percent concentration of NaOH is 9.80%; The cellulose solution that obtains solidifies in first coagulating bath; It is 600mm that tube length degree (the dipping bath degree of depth) is bathed in first coagulating bath; The coagulation bath temperature of first coagulating bath is 50 ℃, and wherein, the mass percent concentration of urea is 0.5%; The mass percent concentration of NaOH is 0.9%, and the coagulating bath flow is 25 times of cellulose solution volume flow; After getting into the godet roller drawing-off, solid-state fiber after spinning machine spinning head place coagulating tank solidifies for the first time in second coagulating bath, solidifies again; Obtain cellulose fibre through follow-up processing again; Wherein, the sulfuric acid that consists of 6wt% concentration of second coagulating bath, coagulation bath temperature are 96 ℃.The over dry intensity of the cellulose fibre that obtains: 1.67cN/dtex.
Claims (9)
1. the method for a cellulose solution solidification forming comprises the steps:
(1) cellulose pulp is dissolved in the mixed aqueous solution of urea or thiocarbamide, alkali metal hydroxide and water composition, obtains cellulose solution;
(2) cellulose solution that obtains of step (1) solidifies in first coagulating bath; The composition of described first coagulating bath comprises the mixed aqueous solution that urea/sulphur urea, alkali metal hydroxide and water are formed; Temperature is 50～100 ℃; Wherein, the concentration of urea/sulphur urea and alkali metal hydroxide is lower than the corresponding used concentration of component of step (1), does not have the adding of acidic materials in first coagulating bath;
(3) the solid-state fiber behind final the curing carries out drawing-off, cut-out, refining, oven dry, packing process and obtains cellulose fibre.
2. method according to claim 1 is characterized in that, the mass percent concentration of urea or thiocarbamide is 0～1% in the middle coagulating bath of step (2), preferred 0.4%.
3. method according to claim 1 and 2 is characterized in that, the mass percent concentration of alkali metal hydroxide is 0～1% in the middle coagulating bath of step (2), preferred 0.3%.
4. method according to claim 1 is characterized in that, in the step (1), the mass percent concentration of alkali metal hydroxide is 5～10%, and the mass percent concentration of urea/sulphur urea is 6～13%.
5. method according to claim 1 is characterized in that, between step (2), (3), also comprises the steps:
(a) the solid-state fiber after step (2) is solidified is through solidifying wherein in second coagulating bath after the drawing-off, and the inorganic acid that consists of 1～10wt% concentration of described second coagulating bath, coagulation bath temperature are 60～100 ℃, and preferred, described inorganic acid is a sulfuric acid.
6. method according to claim 1 is characterized in that, between step (2), (3), also comprises the steps:
(a) the solid-state fiber after step (2) is solidified is through solidifying in second coagulating bath after the drawing-off, and wherein, the inorganic acid that consists of 1～10wt% concentration of described second coagulating bath, coagulation bath temperature are 60～100 ℃, and preferred, described inorganic acid is a sulfuric acid;
(b) the solid-state fiber after step (a) is solidified needs a drawing-off at least; Solid-state fiber carries out drawing-off in the 3rd coagulating bath; Carry out drawing-off again, go cut-out, refining, oven dry, packing process to obtain cellulose fibre, wherein, described the 3rd coagulating bath is that temperature is 60～100 ℃ water or a water vapour; It is preferred, and temperature is 95 ℃ a water.
7. method according to claim 1 is characterized in that, in first coagulating bath, the tow traffic direction is consistent with the body lotion flow direction.
8. method according to claim 1 is characterized in that, the pipe range that solidifies of first coagulating bath is 600～1500mm, preferred 1000～1200mm.
9. according to claim 1 or 8 described methods, it is characterized in that the coagulating bath flow is greater than 20 times of the cellulose solution volume flow, preferred 30-40 doubly.
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| CN110577667A (en) * | 2018-06-08 | 2019-12-17 | 淮安市冰青建设工程管理有限公司 | Cellulose foam material |
| CN110577651A (en) * | 2018-06-08 | 2019-12-17 | 淮安市冰青建设工程管理有限公司 | Preparation method of cellulose solution |
| CN110577668A (en) * | 2018-06-08 | 2019-12-17 | 淮安市冰青建设工程管理有限公司 | Cellulose solution |
| CN110577664A (en) * | 2018-06-08 | 2019-12-17 | 淮安市冰青建设工程管理有限公司 | Preparation method of cellulose foam material |
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| CN1594680A (en) * | 2004-06-29 | 2005-03-16 | 武汉大学 | Preparation method for regenerated cellulose fiber |
| CN1702201A (en) * | 2005-05-30 | 2005-11-30 | 武汉大学 | Method for preparing regenerative cellulose fiber by two-step coagulating bath process |
| CN101429682A (en) * | 2008-11-28 | 2009-05-13 | 东华大学 | Method for producing regenerated cellulose fiber by dual-bath coagulation |
| CN101492837A (en) * | 2009-03-03 | 2009-07-29 | 江苏盛丰登泰生物技术有限公司 | Process for producing bacteria cellulose fibre with high degree of polymerization |
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| CN110577667A (en) * | 2018-06-08 | 2019-12-17 | 淮安市冰青建设工程管理有限公司 | Cellulose foam material |
| CN110577651A (en) * | 2018-06-08 | 2019-12-17 | 淮安市冰青建设工程管理有限公司 | Preparation method of cellulose solution |
| CN110577668A (en) * | 2018-06-08 | 2019-12-17 | 淮安市冰青建设工程管理有限公司 | Cellulose solution |
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