CN116575147A - Preparation method and system of continuous spinning chitosan filaments - Google Patents
Preparation method and system of continuous spinning chitosan filaments Download PDFInfo
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- CN116575147A CN116575147A CN202310640291.XA CN202310640291A CN116575147A CN 116575147 A CN116575147 A CN 116575147A CN 202310640291 A CN202310640291 A CN 202310640291A CN 116575147 A CN116575147 A CN 116575147A
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- 229920001661 Chitosan Polymers 0.000 title claims abstract description 110
- 238000009987 spinning Methods 0.000 title claims abstract description 108
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 86
- 238000003756 stirring Methods 0.000 claims abstract description 40
- 238000001035 drying Methods 0.000 claims abstract description 26
- 238000001914 filtration Methods 0.000 claims abstract description 25
- 239000002253 acid Substances 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 230000006196 deacetylation Effects 0.000 claims abstract description 8
- 238000003381 deacetylation reaction Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 64
- 238000000034 method Methods 0.000 claims description 38
- 239000007921 spray Substances 0.000 claims description 34
- 238000003860 storage Methods 0.000 claims description 34
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- 238000004519 manufacturing process Methods 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 17
- 230000001112 coagulating effect Effects 0.000 claims description 17
- 239000002202 Polyethylene glycol Substances 0.000 claims description 15
- 229920001223 polyethylene glycol Polymers 0.000 claims description 15
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 8
- 239000001632 sodium acetate Substances 0.000 claims description 8
- 235000017281 sodium acetate Nutrition 0.000 claims description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 230000001172 regenerating effect Effects 0.000 claims description 3
- 229940113115 polyethylene glycol 200 Drugs 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 14
- 238000010924 continuous production Methods 0.000 abstract description 7
- 239000000243 solution Substances 0.000 description 44
- 239000000835 fiber Substances 0.000 description 43
- 238000005345 coagulation Methods 0.000 description 14
- 230000015271 coagulation Effects 0.000 description 14
- 239000003513 alkali Substances 0.000 description 13
- 238000004090 dissolution Methods 0.000 description 12
- 239000008041 oiling agent Substances 0.000 description 10
- 230000008929 regeneration Effects 0.000 description 10
- 238000011069 regeneration method Methods 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000007654 immersion Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 4
- 238000009776 industrial production Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000002166 wet spinning Methods 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 239000002216 antistatic agent Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000010041 electrostatic spinning Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000012681 fiber drawing Methods 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 230000002439 hemostatic effect Effects 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/06—Washing or drying
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D4/00—Spinnerette packs; Cleaning thereof
- D01D4/02—Spinnerettes
- D01D4/022—Processes or materials for the preparation of spinnerettes
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Artificial Filaments (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Abstract
The invention discloses a preparation method and a system for continuously spinning chitosan filaments, and belongs to the technical field of chitosan spinning. Adding chitosan raw materials with the viscosity of 450-550 mPa.s and the deacetylation degree of 87.2% into a stirring tank filled with acid liquor, stirring and dissolving, and controlling the concentration of the chitosan solution to be 3.0-3.5 and wt%; filtering, preserving heat and temporarily storing to obtain spinning solution; then, the yarn is led into a spinning tank to be spun at a spinning speed of 30-40 m/min and a draft ratio of 20-30%, and the yarn is obtained; and then sequentially passing through a traction device, a washing device, a steam drying device and a tube forming device to obtain the chitosan filament. Based on a matched preparation system, the stable spinning process is ensured, the yield is high, and the yarn washing effect is good; and the spinning period is short, and industrial continuous production can be realized.
Description
Technical Field
The invention particularly relates to a preparation method and a system for continuously spinning chitosan filaments, and belongs to the technical field of chitosan spinning.
Background
As the only alkaline natural polysaccharide in the nature, the chitosan is safe and nontoxic, and has good biocompatibility, biodegradability, antibacterial property, hemostatic property and the like. The chitosan fiber obtained by dissolution and regeneration can be used for preparing medical gauze, bandages, protective clothing and the like, and has good application prospect in the biomedical field.
At present, the production method of chitosan fiber mainly comprises electrostatic spinning and wet spinning.
1. Electrostatic spinning is difficult to prepare chitosan fibers by electrostatic spinning because electrostatic repulsive force on chitosan molecular chains can prevent the formation of the electrospun fibers under the condition of high electrostatic voltage;
2. in wet spinning, chitosan is generally dissolved in a dilute acid aqueous solution and regenerated by alkali liquor, however, in the wet spinning process, the high-concentration chitosan solution has poor spinnability, the whole spinning process flow period is long, and the chitosan fiber is difficult to control in the post-treatment process. Meanwhile, when the alkali liquor on the silk is removed by adopting a soaking mode, the alkali removal effect is poor, and the alkali liquor on the silk can be removed only after a long time, so that the production efficiency is low. In addition, for the production of chitosan filaments, the problems of filament separation and filament breakage are easy to occur in the filament drawing process, so that the spinning process is unstable, the fiber quality is low, and the like.
The prior art 'CN 106591980' is a chitosan fiber one-step spinning device which comprises a spinning forming mechanism, a tow processing mechanism and a winding recovery mechanism which are sequentially connected from front to back, and the device can realize one-step spinning, but has the following defects: the related regenerated water washing device is a partitioned treatment roller, a fiber drawing process cannot be realized in a water washing section, and the process adjustability is poor; and, failure to achieve systematic, continuous production (e.g., no involvement of oiling, drying, etc.); in the method for preparing the chitosan fiber, the chitosan is dissolved in oxalic acid solution, and then the chitosan fiber is obtained after spinning, washing, baking, drying and cutting. But has the following disadvantages: (1) the coagulating bath is ammonia water with the mass fraction of 4-8% preheated to 35-40 ℃, the ammonia water has volatility, ammonia gas can be formed after volatilization, the irritation is strong, and damage to organs and skin of a human body can be caused, so that the scheme is not suitable for industrial production; (2) and, adopt the absolute ethyl alcohol to soak and wash in the washing process, because ethanol is volatile, its steam and air can form explosive mixture, meet open fire, high heat cause explosion, use the ethanol to have very big potential safety hazard in the production, therefore, is not suitable for the industrial production either; "CN109576803A is a production method of chitosan fiber", which is suitable for the production of chitosan short fiber and can not realize the continuous production of chitosan filament; and, the drying mode involved is freeze-drying, however, freeze-drying has high equipment requirements, low drying efficiency, inability to achieve rapid drying, high energy consumption, and unsuitability for industrial production and the like.
Disclosure of Invention
In order to solve the problems that the preparation process of chitosan filaments in the prior art cannot realize continuous and industrial production and the like, the invention provides a preparation method and a system of continuous spinning chitosan filaments. Based on a matched preparation system, the stable spinning process is ensured, the yield is high, and the yarn washing effect is good; and the spinning period is short, and industrial continuous production can be realized.
In order to achieve the technical purpose, the following technical scheme is provided:
the first object of the present technical solution is to provide: a method for preparing continuous spinning chitosan filaments, comprising the following steps:
1. preparation of spinning solution
1) Dissolving: adding chitosan raw materials with the viscosity of 450-550 mPa.s and the deacetylation degree of 87.2% into a stirring tank filled with acid liquor, controlling the temperature in the stirring tank to be 40-50 ℃ and the stirring speed to be 200 rpm, and carrying out vacuum stirring for 3 h to obtain chitosan solution with the concentration of 3.0-3.5 wt%;
wherein, chitosan with the viscosity of 450-550 mPa.s and the deacetylation degree of 87.2% is selected as a raw material, which is suitable for the subsequent procedures and the control conditions, such as the solubility in the corresponding solvent, namely the influence on the spinning solution; on the other hand, the strength and the functionality of the final product chitosan filament are ensured, wherein the viscosity of the raw material is the expression of the molecular weight of the chitosan, the strength of the filament is greatly influenced, the solubility of the chitosan is also influenced, and the deacetylation degree is related to the antibacterial property of the fiber;
the acid solution is acetic acid solution with the concentration of 1.0-2.0 wt percent, hydrochloric acid with the concentration of 1.0-2.0 weight percent or citric acid solution with the concentration of 6-8 wt percent. Because chitosan is protonated to form-NH through amino groups on the molecular chain when dissolved in acid solution 4 + The dissolution is caused by electrostatic repulsion, wherein if the concentration of the acid solution is low, the amino groups on the chitosan molecular chain can not be fully protonated, the chitosan can not be fully dissolved, and meanwhile, the solubility of the chitosan is reduced due to the low concentration of the acid solution; if the concentration of the acid solution is higher, the chitosan dissolution is not affected, but the production cost is increased, and more alkali is consumed in the subsequent coagulating bath. The concentration of the acid-soluble chitosan of different types is different, which is mainly related to the capability of the acid to ionize H < + >, therefore, the dissolving capability, cost and the like of the chitosan are comprehensively considered, more preferably, the acid solution is acetic acid solution with the concentration of 1.0-2.0 wt%;
in the stirring tank, the temperature is controlled to be 40-50 ℃ and the stirring speed is controlled to be 200 rpm, and the vacuum stirring is carried out for 3 h, the temperature is limited, so that the chitosan can achieve better dissolution effect under the condition of ensuring no obvious degradation. Because the viscosity of the chitosan solution can be reduced along with the temperature rise, if the temperature is lower during dissolution, the solution viscosity is relatively higher, the stirring resistance during dissolution is increased, the stirring effect is poor, the final dissolution effect is poor, and the subsequent processes such as filtration, spinning and the like are affected; if the temperature is too high during dissolution, chitosan can be obviously degraded, so that the stability of the subsequent process and the quality of the final product are affected, and therefore, the temperature in the stirring tank is controlled to be 40-50 ℃ after all factors are combined. Because the viscosity of the chitosan solution is high, if the stirring speed is too high, the running load of equipment can be increased, and even a motor can be burnt out; if the stirring speed is too low, a relatively good dissolution effect cannot be achieved, and the chitosan is insufficiently dissolved to affect the subsequent spinning, so that the stirring speed is 200 rpm. Vacuum stirring is carried out for 3 h, so that the chitosan is fully dissolved, if the stirring time is too long, the running cost of equipment is increased, the dissolution effect of the chitosan is not obviously improved, and the significance is not great;
according to the common knowledge in the technical field, the concentration of the chitosan solution changes along with the viscosity change of the raw materials, and if the viscosity of the raw materials is high, the concentration of the chitosan solution is lower; the raw material viscosity is low, so that the concentration of the chitosan solution is higher, thereby ensuring that the rotational viscosity index of the chitosan solution obtained by dissolution is kept consistent. Because the chitosan raw material with the viscosity of 450-550 mPa.s and the deacetylation degree of 87.2% is selected, after the chitosan raw material is dissolved, the concentration of the corresponding chitosan solution is 3.0-3.5-wt%, and the influence of the viscosity index fluctuation of the raw material on the subsequent process flow can be effectively avoided by adjusting and controlling the concentration and the viscosity, namely the stable operation of the subsequent process flow is facilitated;
2) And (3) filtering: filtering the chitosan solution by adopting a filter screen with the aperture of 15 mu m; then, storing the filtrate in a temporary storage tank with a jacket, and introducing water at 50 ℃ into the jacket for heat preservation to obtain spinning solution;
the filter screen with the aperture of 15 mu m is adopted, so that smaller impurities can be intercepted, the impurity removal is ensured to be sufficient, the filtering effect is improved, and the subsequent spinning is facilitated. If the impurities are not sufficiently removed during filtration, the spinning process is greatly affected, and even the phenomena of yarn separation and yarn breakage occur due to the impurities;
2. spinning process
Introducing the obtained spinning solution into a spinning tank with a jacket, and introducing water at 50 ℃ into the jacket to keep the temperature so as to ensure the fluidity of the spinning solution;
extruding the solution by compressed air, and adopting a large Kong Huang platinum spray head (30 holes) with a spray hole aperture of 0.078 and mm, wherein the spray head is made of platinum: gold = 4:6; spinning at a spinning speed of 30-40 m/min and a draft ratio of 20-30%. When the spray head is selected, corrosion resistance of spray head materials to acid and alkali is mainly considered, and as long as the conditions can be met, spray heads made of other materials can be used. The size of the nozzle aperture is mainly related to the thickness of the spun silk bundle, and the nozzle with the corresponding aperture can be selected according to actual requirements. In addition, "spinning speed is 30-40 m/min, draft ratio is 20-30%", under the premise of guaranteeing spinning quality, spinning efficiency is improved, for example: if the spinning speed is too low, the production efficiency is low, and the production cost is high; if the spinning speed is too high, the conditions of yarn separation and yarn breakage will occur, and based on the conditions, the spinning speed is improved as much as possible on the premise of ensuring the stable spinning process. Wherein, the drafting can promote the performance of chitosan filament, if the drafting condition is lower, the strength of the filament is lower, but the spinning is not influenced (the drafting ratio can be even 0%); if the drawing conditions are higher than the above-mentioned drawing conditions, the filament may be split and broken during the drawing process;
wherein the coagulating bath comprises 3-5 wt% of sodium hydroxide, 10-20 wt% of sodium acetate and 20-40 wt% of polyethylene glycol, the coagulating bath temperature is 30-40 ℃, and the soaking length of the silk is 500-1000 mm. The conventional regeneration mode of chitosan in an acid solution solvent system adopts 'acid-soluble alkali coagulation', namely, alkali coagulation bath is used for regeneration, sodium hydroxide is a common alkali, the cost is relatively low, and KOH and LiOH can also be used, but the cost is relatively high; the sodium acetate is selected to be added, the regeneration rate of the fiber can be slowed down due to the existence of salt, so that the performance of the filament is improved, and the sodium acetate is generated in the process of reacting with sodium hydroxide in the coagulating bath due to the fact that the solvent selected during dissolution is acetic acid, namely, other chemical substances are not introduced, so that the complexity of a system is prevented from being increased; the introduction of polyethylene glycol can not only further delay the regeneration rate of the fiber, but also effectively improve the strength and the extensibility of the filament and the spinnability, and can also increase the softness of the fiber (the polyethylene glycol has the effect of a softener);
the coagulating bath temperature is 30-40 ℃, and the limiting of the coagulating bath temperature is convenient for controlling the regeneration rate of the fiber and ensuring the fiber performance. Too high a temperature, fast molecular movement and too fast fiber regeneration rate can lead to the decrease of fiber performance; the temperature is too low, the fiber regeneration rate is too slow, and the subsequent processes such as drawing the fiber are not facilitated;
the immersion length of the yarn is 500-1000 mm, and the yarn can be fully regenerated and formed in a coagulating bath. If the immersion length is too short, the reaction of the silk in the forming process is insufficient, and the performance of the silk is affected; the fiber is completely solidified due to the overlong soaking length, and the subsequent drafting process can be influenced, so that the yarn performance is influenced. In addition, the excessive immersion length can also lead the strand silk to carry more alkali away from the coagulating bath, which can influence the subsequent water washing process, namely, lead to insufficient water washing and the like;
and (5) enabling the spun yarn to pass through a traction device, a washing device and a steam drying device and then to reach a barrel forming device to obtain the chitosan filament.
Further, the polyethylene glycol is polyethylene glycol 200.
The second object of the present technical solution is to provide: a continuous spinning chitosan filament preparation system comprises a stirring tank, a filtering device, a temporary storage tank, a spinning device, a traction device, a washing device, a steam drying device and a tube forming device, wherein,
a stirring tank: comprises a tank body and a stirring mechanism arranged in the tank body, wherein the tank body is provided with a raw material port and an acid liquid port; the tank body is connected with a vacuum system;
a filtering device: comprises a filter screen with a pore diameter of 15 mu m;
temporary storage tank: the outside is sleeved with a heat-insulating jacket, and water at 50 ℃ is arranged in the jacket;
spinning device: comprises a spinning tank, a spinneret, a coagulating bath and a regenerating bath;
traction device: comprises a guide wheel, a traction roller and a drafting roller;
washing device: comprises a water washing mechanism and an oil applying mechanism; a water washing spray head is arranged above each water washing area in the water washing mechanism, a water storage tank is arranged below the water washing spray head, and a water inlet pipe of the water washing spray head is communicated with the water storage tank; an oil feeding nozzle is arranged above each oil feeding area in the oil feeding mechanism, an oil storage tank is arranged below the oil feeding area, and an oil inlet pipe of the oil feeding nozzle is communicated with the oil storage tank;
the yarn formed in the spinning device sequentially passes through a traction device, a washing device and a steam drying device and then reaches a cylinder device;
a passage for continuously preparing chitosan filaments is formed among the stirring tank, the filtering device, the temporary storage tank, the spinning device, the traction device, the washing device, the steam drying device and the tube forming device.
Furthermore, the number of the water washing areas in the water washing mechanism is 4-10, water washing spray heads are arranged above each water washing area, water storage tanks are correspondingly arranged below each water washing spray head, and the water temperature of the water washing areas is 40-60 ℃.
Further, the number of the oiling areas in the oiling mechanism is 1-3, oiling spray heads are arranged above each oiling area, oil storage tanks are correspondingly arranged below each oiling spray head, and the oil temperature of each oiling area is 50 ℃.
In the technical scheme, the relation of the front side of the station, the rear side of the station, the relation between the stations, the inner side, the upper side, the outer side, the upper side, the lower side and the like is defined according to the condition in the actual use state, is a conventional term in the technical field, and is also a conventional term in the actual use process of a person skilled in the art.
By adopting the technical scheme, the beneficial technical effects brought are as follows:
1. the invention provides a proper treatment procedure and matched control conditions based on wet spinning, ensures that the spinning process is simple, easy to operate, stable, high in yield and good in strand silk washing effect; the continuous spinning equipment is adopted, so that the short spinning period is ensured, the process is stable, the related production cost is lower, the mass production is convenient, the industrial continuous production can be realized, and the economic benefit is great.
Wherein, in the coagulating bath, besides the conventional alkali and salt, the organic solvent polyethylene glycol is introduced, so that the polyethylene glycol not only can delay the regeneration rate of the fiber more gently, effectively improve the strength and depth of the fiber, but also can improve the spinnability and the softness of the fiber;
2. the invention also provides a preparation system which is suitable for the rapid and continuous production of chitosan filaments, and the device has simple structure, stable work and high production efficiency;
in the washing process stage, the silk strips can be quickly washed by adopting a hot water leaching mode, so that the whole production efficiency is improved; in the oiling process stage, two oiling steps are adopted: an antistatic agent is adopted in the oiling agent, so that the electrostatic effect existing among chitosan fibers can be effectively reduced; the other oiling agent adopts a conventional filament oiling agent, so that the softness of the fiber can be effectively improved; and multistage drafting is further arranged between the washing areas in the washing equipment by adjusting the speed of the rollers, so that the fiber strength and the like are further improved.
Drawings
FIG. 1 is a block diagram of a manufacturing system according to the present invention;
FIG. 2 is a schematic illustration of the process of forming a yarn according to the present invention;
FIG. 3 is a physical diagram of the chitosan filaments prepared by the invention;
in the figure, 1, a spinneret, 2, a coagulating bath, 3, a guide wheel, 4, a traction roller, 5, a traction roller, 6, a water washing spray head, 7, a water storage tank, 8, a water washing mechanism, 9, an oiling spray head, 10, an oil storage tank, 11, an oiling mechanism, 12, a steam drying device, 13, a tube forming device, 14, a stirring tank, 15, a filtering device, 16, a temporary storage tank, 17, a spinning device, 18, a traction device, 19 and a washing device.
Detailed Description
In the following, it is obvious that the embodiments described are only some embodiments of the present invention, but not all embodiments, by clearly and completely describing the technical solutions in the embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation method of the continuous spinning chitosan filament provided by the embodiment comprises the following steps:
(1) Preparing spinning solution: an industrial chitosan raw material having a viscosity of 450 mpa.s (degree of deacetylation: 87.2%) was added to a stirring tank 14 containing 2 wt% aqueous acetic acid, and the mixture was vacuum-pumped and stirred for 3 h to obtain a chitosan solution having a concentration of 3.5wt%, an aqueous acetic acid concentration of 2.0wt%, an aqueous acetic acid temperature of 45 ℃ and a stirring speed of 200 rpm. Filtering the chitosan solution, wherein the size of a filter screen is 15 mu m, storing the filtered chitosan solution in a storage tank with a jacket, and introducing water at 50 ℃ into the jacket for heat preservation;
(2) The spinning process comprises the following steps: the filtered solution was introduced into a spinning pot with a jacket through which water at 50℃was passed for heat preservation. Extruding the solution by compressed air, and adopting a large Kong Huang platinum spray head (30 holes) with a spray hole aperture of 0.078 and mm, wherein the spray head is made of platinum: gold=4:6, spinning speed 30 m/min, draft ratio 20%. The coagulation bath 2 is as follows: naOH content 3 wt%, sodium acetate 15 wt%, polyethylene glycol 40 wt%, coagulation bath 2 temperature 30 ℃ and filament immersion length 800 mm. The spun yarn passes through a traction device 18, a washing device 19 and a steam drying device 12 and then reaches a barrel forming device, thus obtaining chitosan filaments.
At present, the chitosan spinning process flow is generally longer in period, the technical scheme adopted by the method is short in process flow, the spinning process method is simple, easy to operate and stable, continuous spinning equipment is adopted for spinning, the chitosan fiber production efficiency can be greatly improved, and the whole spinning period is greatly shortened. In addition, because the wet strength of the chitosan filaments is low, the problems of filament separation and filament breakage of the solution easily occur in the spinning process, and therefore, in the coagulation bath 2 used in the embodiment, besides conventional alkali and salt, the polyethylene glycol which is an organic solvent is introduced, so that the polyethylene glycol not only can delay the regeneration rate of the fibers more gently, but also can effectively improve the strength and depth of the fibers, improve the spinnability and also increase the softness of the fibers.
Example 2
On the basis of the embodiment 1, the embodiment provides a preparation system of continuous spinning chitosan filaments, which is suitable for the preparation of continuous spinning chitosan filaments, as shown in fig. 1-2, and comprises: the device comprises a stirring tank 14, a filtering device 15, a spinning device 17, a traction device 18, a washing device 19, a steam drying device 12 and a drum forming device 13, wherein the stirring tank 14 is arranged on the front side of a station of the filtering device 15, the spinning device 17 is arranged on the rear side of the station of the filtering device 15, the traction device 18 is arranged on the rear side of the station of the spinning device 17, the washing device 19 is arranged on the rear side of the station of the traction device 18, the steam drying device 12 is arranged on the rear side of the station of the washing device 19, and the drum forming device 13 is arranged on the rear side of the station of the steam drying device 12; a temporary storage tank 16 is arranged between the filtering device 15 and the spinning device 17; wherein, the liquid crystal display device comprises a liquid crystal display device,
stirring tank 14: comprises a tank body and a stirring mechanism arranged in the tank body, wherein the tank body is provided with a raw material port and an acid liquid port; the tank body is connected with a vacuum system;
filter device 15: comprises a filter screen with a pore diameter of 15 mu m;
temporary storage tank 16: the outside is sleeved with a heat-insulating jacket, and water at 50 ℃ is arranged in the jacket;
spinning device 17: comprises a spinning tank, a spinneret 1, a coagulating bath 2 tank and a regenerating bath tank;
traction device 18: comprises a guide wheel 3, a traction roller 4 and a drafting roller 5;
washing device 19: comprises a water washing mechanism 8 and an oiling mechanism 11; a water washing spray head 6 is arranged above each water washing area in the water washing mechanism 8, a water storage tank 7 is arranged below the water washing spray head, and a water inlet pipe of the water washing spray head 6 is communicated with the water storage tank 7; an oil feeding spray head 9 is arranged above each oil feeding area in the oil feeding mechanism 11, an oil storage tank 10 is arranged below the oil feeding spray head, and an oil inlet pipe of the oil feeding spray head 9 is communicated with the oil storage tank 10;
the yarn formed in the spinning device 17 passes through the drawing device 18, the washing device 19 and the steam drying device 12 in sequence, and then reaches the drum forming device 13;
a passage for continuously preparing chitosan filaments is formed among the stirring tank 14, the filtering device 15, the temporary storage tank 16, the spinning device 17, the traction device 18, the washing device 19, the steam drying device 12 and the tube forming device 13.
The related working process is as follows:
in the spinning device 17, the chitosan solution is extruded from the spinneret 1, regenerated in the coagulation bath 2 to obtain a molded yarn, and enters the traction device 18 through the guide wheel 3; the silk in the traction device 18 firstly passes through the traction roller 4 and then reaches the traction roller 5, wherein the speed of the traction roller 4 is V1 = 25 m/min, the speed of the traction roller 5 is V2 = 30 m/min, and the silk enters the washing device 19 after being drafted in the process; the washing device 19 comprises a washing mechanism 8 and an oiling mechanism 11, wherein the washing mechanism 8 comprises 4-10 washing areas, preferably 5 washing areas, a washing spray head 6 is arranged above each washing area, a water storage tank 7 is arranged below each washing area, and the water temperature of the washing areas is 45 ℃; the oiling mechanism 11 comprises 1-3 oiling areas, preferably 2 oiling areas, wherein an oiling spray head 9 is arranged above each oiling area, an oil storage tank 10 is arranged below each oiling area, the oil temperature of each oiling area is 50 ℃, the oiling agents used in the two oiling areas are different, one of the oiling agents is an antistatic agent, and the other oiling agent is a conventional filament oiling agent; the silk strip enters a steam drying device 12 after being washed and oiled, and reaches a barrel forming device 13 for barrel forming after being dried.
The chitosan spinning is usually soaked in the water washing working section, the water washing efficiency is low, the water consumption is high, and the water washing efficiency is greatly improved and the water cost is saved by adopting the hot water spraying mode in the embodiment;
the chitosan fiber in the prior art has higher production cost, the process flow related to the embodiment is simple, a large amount of labor cost can be saved, and meanwhile, the washing efficiency is high, so that the production water cost can be greatly saved;
at present, the prior art for producing chitosan filaments by adopting continuous spinning equipment is less, and the technical scheme combines the continuous spinning equipment and a matched and adaptive process method, thereby achieving the aim of rapidly producing chitosan filaments.
Example 3
The embodiment provides a preparation method of continuous spinning chitosan filaments. The preparation system comprises a spinning device 17, a traction device 18, a washing device 19, a steam drying device 12 and a drum forming device 13.
First, an industrial-grade chitosan raw material (viscosity 450 mPa.s, degree of deacetylation 87.2%) of 0.7. 0.7 kg was charged into a stirring tank 14 containing a 2. 2 wt% aqueous acetic acid solution of 19.3. 19.3 kg, and vacuum-stirred (stirring speed 200 rpm) for 3 h to obtain a chitosan solution having a concentration of 3.5 wt%.
Then, the chitosan solution was filtered, the size of the filter screen was 15 μm, and the filtered chitosan solution was stored in a jacketed storage tank for spinning (jacket was kept warm by passing 50 ℃ C. Water). The chitosan solution was extruded from spinneret 1 (orifice diameter 0.078 mm,30 holes) by compressed air, and regenerated in coagulation bath 2 (bath temperature 30 ℃ C., immersion length 800 mm) to obtain a molded yarn, wherein the coagulation bath 2 comprises the following components: naOH content 3 wt%, sodium acetate 15 wt% and polyethylene glycol 40 wt%.
The formed yarn enters a washing mechanism 8 in a washing device 19 through a guide wheel 3, a traction roller 4 and a drafting roller 5, wherein the speed V1 of the traction roller 4 is equal to or less than 25 m/min, the speed V2 of the drafting roller 5 is equal to or less than 30 m/min, and the yarn draft ratio is 20%. The silk strip is oiled after passing through 5 washing areas (water temperature is 45 ℃) in the washing mechanism 8, a washing spray head 66 is arranged above each washing area, and a water storage tank 7 is arranged below each washing area and used for circulation. The oiling mechanism 11 comprises 2 oiling areas (the oil temperature is 50 ℃), an oiling spray head 9 is arranged above each oiling area, an oil storage tank 10 is arranged below each oiling area and used for circulation, the oiling agent used in one oiling area is an antistatic agent, and the oiling agent used in the other oiling area is a conventional filament oiling agent.
The silk is washed and oiled, then enters a steam drying device 12 for drying, and the dried silk is wound into a tube in a tube forming device 13, so that chitosan filaments (figure 3) are obtained. Wherein, detect the end product chitosan filament, obtain: the fineness of the filaments was 1.55 dtex, the breaking strength of the fibers was 1.81 cN/dtex, the elongation at break of the fibers was 7.7%, and the antibacterial rate of the fibers was 95.3% (against Staphylococcus aureus), as shown in Table 1.
Examples 4 to 12
Examples 4-12 respectively provide a method for preparing continuous spinning chitosan filaments, which is different from example 3 in that: the composition of the coagulation bath 2, the speed of the drawing roll 4 and the speed of the drawing roll 5 were varied, and other process and equipment parameters were consistent with example 3 and will not be described again. The corresponding parameters for examples 4-12 are shown in Table 2 below.
According to the same production method as in example 3, chitosan filaments were produced by the processes provided in examples 4 to 12, respectively, and the properties of the chitosan filaments produced in each example were examined, and the results are shown in the following table 3.
It can be seen in combination with tables 2-3 that: the components of the coagulating bath and the spinning technological parameters in the preparation process are changed, so that the properties of the chitosan filaments of the final product can be regulated and controlled.
In summary, it can be seen that:
1. in combination with examples 3-5, too high or too low a concentration of sodium acetate in the coagulation bath will decrease the strength of the fiber;
2. in combination with examples 3, 6-7, too high a concentration of alkali in the coagulation bath also reduces the strength of the fiber;
3. in combination with examples 3 and 8-10, the introduction of polyethylene glycol can effectively improve the strength and the extensibility of the fiber, but the higher concentration of polyethylene glycol can also increase the resistance in the coagulation bath, so that the strength of the fiber is reduced;
4. by combining examples 3 and examples 11-12, increasing the draw ratio is effective in increasing the fiber strength, but significantly reduces the fiber elongation;
5. in combination with examples 3-12, changing the composition of the coagulation bath and the spinning process parameters during the fiber preparation had no significant effect on the antimicrobial rate of the fiber.
Therefore, in order to ensure that the prepared chitosan filaments have better comprehensive performance, the preferred coagulation bath components of the invention are NaOH content 3 wt percent, sodium acetate 15 wt percent, polyethylene glycol 40 wt percent and preferred traction roller speed V 1 Draft roller speed V =25 m/min 2 =30 m/min, draft ratio was 20%.
Claims (10)
1. A method for preparing continuous spinning chitosan filaments, which is characterized by comprising the following steps:
1) Dissolving: adding chitosan raw materials with the viscosity of 450-550 mPa.s and the deacetylation degree of 87.2% into a stirring tank (14) filled with acid liquor, stirring and dissolving, and controlling to obtain chitosan solution with the concentration of 3.0-3.5 and wt%;
2) And (3) filtering: filtering the obtained chitosan solution, and then preserving heat and temporarily storing to obtain spinning solution;
3) Spinning: introducing the obtained spinning solution into a spinning tank, spinning at a spinning speed of 30-40 m/min and a draft ratio of 20-30% to obtain a yarn;
wherein the coagulating bath (2) comprises 3-5 wt% of sodium hydroxide, 10-20 wt% of sodium acetate and 20-40 wt% of polyethylene glycol, the temperature of the coagulating bath (2) is 30-40 ℃, and the soaking length of the silk is 500-1000 mm;
4) Post-treatment: the obtained filament is passed through a traction device (18), a washing device (19) and a steam drying device (12) to a cylinder device (13) to obtain chitosan filament.
2. The method of producing continuous spinning chitosan filaments according to claim 1, wherein in step 1), the dissolving comprises: the temperature in the stirring tank (14) is controlled to be 40-50 ℃ and the stirring speed is controlled to be 200 rpm, and 3-h is stirred under vacuum condition.
3. The method for producing continuous spinning chitosan filaments according to claim 1, wherein in step 1), the acid solution is an acetic acid solution having a concentration of 1.0 to 2.0wt%, hydrochloric acid having a concentration of 1.0 to 2.0wt%, or citric acid solution having a concentration of 6 to 8 wt%, preferably, an acetic acid solution having a concentration of 1.0 to 2.0 wt%.
4. The method for producing continuous spinning chitosan filaments according to claim 1, wherein in the step 2), the filtration is performed by using a sieve having a pore size of 15 μm; the heat preservation comprises the following steps: is carried out in a temporary tank (16) with jacketed water at 50 ℃.
5. The method of producing continuous spinning chitosan filaments according to claim 1, wherein in step 3), the polyethylene glycol is polyethylene glycol 200.
6. The method for producing continuous spinning chitosan filaments according to claim 1, characterized in that in step 4), the speed of the drawing roll (4) in the drawing device (18) is 25 m/min and the speed of the drawing roll (5) is 30 m/min.
7. The method for producing continuous spinning chitosan filaments according to any one of claims 1 to 6, wherein the continuous spinning chitosan filaments are produced by a production system comprising: the device comprises a stirring tank (14), a filtering device (15), a spinning device (17), a traction device (18), a washing device (19), a steam drying device (12) and a drum forming device (13), wherein the stirring tank (14) is arranged at the front side of a station of the filtering device (15), the spinning device (17) is arranged at the rear side of the station of the filtering device (15), the traction device (18) is arranged at the rear side of the station of the spinning device (17), the washing device (19) is arranged at the rear side of the station of the traction device (18), the steam drying device (12) is arranged at the rear side of the station of the washing device (19), and the drum forming device (13) is arranged at the rear side of the station of the steam drying device (12);
a temporary storage tank (16) is arranged between the filtering device (15) and the spinning device (17);
the washing device (19) comprises a washing mechanism (8) and an oiling mechanism (11), a washing spray head (6) is arranged above each washing area in the washing mechanism (8), a water storage tank (7) is arranged below the washing area, and a water inlet pipe of the washing spray head (6) is communicated with the water storage tank (7); an oil spraying nozzle (9) is arranged above each oil spraying area in the oil spraying mechanism (11), an oil storage tank (10) is arranged below the oil spraying mechanism, and an oil inlet pipe of the oil spraying nozzle (9) is communicated with the oil storage tank (10);
a passage for continuously preparing chitosan filaments is formed among the stirring tank (14), the filtering device (15), the temporary storage tank (16), the spinning device (17), the traction device (18), the washing device (19), the steam drying device (12) and the tube forming device (13).
8. The method for preparing continuous spinning chitosan filaments according to claim 7, wherein the number of the water washing areas in the water washing mechanism (8) is 4-10, water washing spray heads (6) are arranged above each water washing area, water storage tanks (7) are correspondingly arranged below each water washing spray head (6), and the water temperature of the water washing areas is 40-60 ℃.
9. The preparation method of the continuous spinning chitosan filament according to claim 7, wherein the number of oiling areas in the oiling mechanism (11) is 1-3, oiling spray heads (9) are arranged above each oiling area, an oil storage tank (10) is correspondingly arranged below each oiling spray head (9), and the oil temperature of the oiling area is 50 ℃.
10. The method for preparing continuous spinning chitosan filaments according to claim 7, wherein the stirring tank (14) comprises a tank body and a stirring mechanism arranged in the tank body, and the tank body is provided with a raw material port and an acid liquid port; the tank body is connected with a vacuum system;
the filtering device (15) comprises a filter screen with a pore size of 15 mu m;
the spinning device (17) comprises a spinning tank, a spinning nozzle (1), a coagulating bath (2) tank and a regenerating bath tank;
the traction device (18) comprises a guide wheel (3), a traction roller (4) and a traction roller (5).
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