CN114808173A - Method for preparing green regenerated cellulose fibers by using vinasse as raw material - Google Patents
Method for preparing green regenerated cellulose fibers by using vinasse as raw material Download PDFInfo
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- CN114808173A CN114808173A CN202210283126.9A CN202210283126A CN114808173A CN 114808173 A CN114808173 A CN 114808173A CN 202210283126 A CN202210283126 A CN 202210283126A CN 114808173 A CN114808173 A CN 114808173A
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Images
Classifications
-
- 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
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
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- 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
- D01D1/00—Treatment of filament-forming or like material
- D01D1/02—Preparation of spinning solutions
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
Abstract
The invention relates to a method for preparing green regenerated cellulose fibers by using vinasse as a raw material. The method comprises the following steps: soaking the brewed vinasse in dilute alkali liquor, filtering, washing with water, drying, separating, crushing the obtained vinasse lignocellulose, alkalizing by using alkali liquor, removing lignin, drying, dissolving the obtained vinasse cellulose in a solvent, and spinning. The method starts from the concepts of environmental protection and low-carbon recycling, takes the vinasse as the raw material to prepare the green recycled cellulose fiber, uses the fiber in the field of textiles, develops a high-valued application technical path for changing waste into valuable, and provides technical guidance and theoretical support for the application of the vinasse in the field of the recycled cellulose fiber.
Description
Technical Field
The invention belongs to the field of preparation of functional fibers, and particularly relates to a method for preparing green regenerated cellulose fibers by using vinasse as a raw material.
Background
The regenerated cellulose fiber is most famous as first-generation viscose, second-generation modal and tencel lyocell, has the characteristics of excellent hygroscopicity, comfortableness, skin friendliness and easiness in dyeing similar to those of natural cellulose, and is widely applied to the textile fields of clothes, home textiles and the like. However, the raw materials for preparing the regenerated cellulose are all prepared by using high-quality wood, cotton and cotton linter as raw materials, a large number of raw material sources depend on import, and the raw material sources of products are limited.
The distiller's grains are the residual solid mixture after the fermented grains are distilled, and are the largest by-product in the wine making industry. The vinasse contains rich nutrient substances such as starch, protein, fat and the like, and simultaneously contains a large amount of microorganisms, and if the vinasse cannot be treated in time, the vinasse is easy to mildew and rot, so that the environment is polluted. China is a big country for brewing distilled liquor, the yield of white spirit is huge, and the yield of byproduct vinasse is increased rapidly. According to statistics, 6-10 tons of vinasse can be produced when one ton of white spirit is produced, and the national vinasse yield reaches 1.1 hundred million tons according to the calculation of the white spirit yield in 2018 in China.
The vinasse is used as a brewing byproduct, the recycling value of the vinasse in the brewing industry is not high, and most of the vinasse is treated as livestock feed or raw materials for biogas fermentation. In recent years, a technology for recycling distiller's grains using distiller's grains as a raw material has been widely focused, for example, extraction of chemical raw materials such as phytic acid, glycerol, and xylitol from distiller's grains is used, but in general, development and research for high-value utilization of distiller's grains have not been sufficiently carried out.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for preparing green regenerated cellulose fibers by using vinasse as a raw material so as to fill the blank in the prior art.
The invention provides a method for preparing regenerated cellulose fibers by using vinasse as a raw material, which comprises the following steps:
(1) soaking the vinasse after brewing in dilute alkali liquor, filtering, washing with water, drying, and separating to obtain vinasse lignocellulose;
(2) crushing the vinasse lignocellulose obtained in the step (1), alkalizing by using alkali liquor, and performing lignin removal, washing and drying to obtain the vinasse cellulose;
(3) and (3) dissolving the vinasse cellulose in the step (2) in a solvent, and spinning the obtained vinasse cellulose spinning solution to obtain the regenerated cellulose fiber.
Preferably, the distiller's grains in the step (1) are one of white spirit distiller's grains, beer distiller's grains and beer distiller's grains/white spirit distiller's grains mixed distiller's grains.
More preferably, the vinasse is fen-flavor vinasse in white spirit vinasse.
Preferably, the dilute alkali solution in the step (1) is: sodium hydroxide solution with mass percent concentration of 0.1-1%.
Preferably, the dipping in the step (1) is dynamic stirring dipping, the stirring rotating speed is 200-800RPM, the dipping temperature is 35-60 ℃, the dipping time is 0.5-2h, and the dipping bath ratio is 12-18: 1.
preferably, the filtering and separating in the step (1) are treated by using a 300-mesh stainless steel gauze.
Preferably, deionized water is used for water washing in the step (1).
Preferably, the drying temperature in the step (1) is 50-85 ℃, and the drying time is 3-8 h.
Preferably, the quality fraction of the alkali liquor in the step (2) is 8-14%; the alkalization temperature is 60-90 ℃, the alkalization time is 2-4h, and the alkalization bath ratio is 5-10: 1.
preferably, the delignification process in the step (2) is as follows: adding the alkalized vinasse lignocellulose into a sodium sulfite/sodium hydroxide mixed solution for boiling, wherein the bath ratio is 10-15:1, and the sodium sulfite/sodium hydroxide mixed solution comprises the following components in percentage by mass: 2-3% of sodium hydroxide, 2-5% of sodium sulfite and 92-98% of water; the boiling temperature is 100-150 ℃, and the boiling time is 2-4 h.
Preferably, bleaching is performed after the delignification process in the step (2) is finished, and the bleaching is performed as follows: adding 2-5% hydrogen peroxide and bleaching for 30min or adding sodium hypochlorite and bleaching for 0.5-2 h.
Preferably, the drying in the step (2) is: air-blast drying at 50 ℃.
Preferably, the solvent in step (3) comprises one of a conventional base/urea system, an N-methylmorpholine-N-oxide NMMO system, and an ionic liquid system.
More preferably, the solvent is an N-methylmorpholine-N-oxide NMMO system; the refractive index of the N-methylmorpholine-N-oxide NMMO system is 1.40-1.50. The refractive index is measured by a fully automatic light meter using a Shanghai Zong light meter.
More preferably, the dissolution conditions are: dissolving at 90-130 deg.C under vacuum and reduced pressure for 2-5 h.
More preferably, the solution is defoamed for use.
Preferably, the mass percentage of the vinasse cellulose in the vinasse cellulose spinning solution in the step (3) is 1.5-3%.
Preferably, the spinning in the step (3) is wet spinning or dry-jet wet spinning.
More preferably, the N-methylmorpholine-N-oxide NMMO system adopts dry-jet wet spinning; the dry-jet wet spinning process parameters are as follows: the spinning solution trickles extruded from the capillary holes firstly pass through air and then enter a coagulating bath solution for coagulation forming, washing, drying and winding, wherein the distance of an air section is 100-200mm, the extrusion speed is 1-30m/min, the pore diameter of the capillary holes is 0.06-1.5mm, the temperature of the coagulating bath solution is 35-50 ℃, and the composition of the coagulating bath solution is 5-14% of NMMO/H 2 O system, total draft multiple is 0.5-2.5 times.
The invention also provides the regenerated cellulose fiber prepared by the method.
The invention also provides application of the regenerated cellulose fiber prepared by the method in textiles, for example, the regenerated cellulose fiber can be blended with traditional synthetic fibers and/or natural fibers to form yarn, and the yarn can be woven into fabrics by textile technology and applied to underwear, clothes or home textiles.
The invention deeply excavates the high value-added application potential of the vinasse byproduct as a waste material, develops a method for preparing green regenerated cellulose fiber by using vinasse as a raw material, and then develops the application of the vinasse byproduct in the textile fields of clothes, home textiles and the like.
Advantageous effects
(1) The invention firstly provides a method for preparing green regenerated cellulose fiber by using vinasse as a raw material;
(2) the invention can obviously reduce the production cost of the regenerated cellulose fiber;
(3) the technology for preparing the green regenerated cellulose fibers by taking the vinasse waste as the raw material develops a high-valued application technical path for changing waste into valuable, and provides technical guidance and theoretical support for the application of the vinasse waste in the field of regenerated cellulose fibers;
(4) the prepared regenerated cellulose fiber has excellent mechanical property, soft fabric, good hygroscopicity and excellent antibacterial property.
Drawings
FIG. 1 is a photograph of the morphology of the distillers 'grains cellulose prepared by the present invention, wherein a, original ecology distillers' grains; b. soaking the washed vinasse lignocellulose; c. drying the screened vinasse lignocellulose; d. crushed vinasse lignocellulose; e. and (4) purifying the distilled grain cellulose.
FIG. 2 is a digital photograph of a spinning solution and fibers thereof according to the present invention, wherein a is a distillers' grains cellulose/NMMO solution; b. and regenerating cellulose fiber by using vinasse.
FIG. 3 is an SEM photograph of the internal structure of regenerated cellulose fibers prepared under different coagulation conditions; (a) forming 20% NMMO aqueous solution at 30 ℃; (b) a10% aqueous NMMO solution was formed at 45 ℃.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The sources of the reagents used in the embodiment of the invention are as follows: sodium hydroxide is purchased from a national medicine reagent, NMMO is purchased from an alladin reagent, when the medical wine is used, the medical wine is further evaporated, concentrated and purified to a certain water content (the concentration is calibrated by a refractive index in the embodiment), hydrogen peroxide, sodium hypochlorite and sodium sulfite are purchased from Shanghai Mecline, and vinasse is sourced from a domestic wine factory.
The test method comprises the following steps: (1) and (3) testing mechanical properties: the mechanical property of the hybrid fiber is characterized by using a monofilament strength instrument, and the test conditions are as follows: the fiber holding distance was 20mm, the filament clamping weight was 0.25cN, the drawing speed was 20mm/min, and the average value was taken 10 times of the test.
(2) Moisture absorption test: before testing, the fibers were dried to constant weight and then the prepared fibers were allowed to stand under constant conditions of 90% relative humidity for 24h to allow them to absorb moisture sufficiently. Then the mass before and after moisture absorption is obtained by a weighing method to calculate the moisture absorption of the fiber.
(3) And (3) antibacterial property test: and testing the antibacterial performance of the vinasse regenerated cellulose fiber by adopting an oscillation method according to GBT 20944.3-2008.
Example 1
The embodiment provides a method for preparing green regenerated cellulose fibers by using vinasse as a raw material, which comprises the following steps:
(1) and (3) preparing vinasse lignocellulose, namely soaking the fen-flavor distiller's grains in 0.5 percent sodium hydroxide solution by mass percent, wherein the soaking bath ratio is 12: 1, simultaneously carrying out mechanical stirring, wherein the dipping temperature is 50 ℃, the dipping time is 1.5h, and the stirring rotating speed is 700 RPM. And after the impregnation is finished, filtering by adopting a 300-mesh stainless steel gauze, repeatedly washing with water, filtering again, drying at 60 ℃ for 4 hours, and screening to obtain the vinasse lignocellulose.
(2) Preparing the vinasse lignocellulose, namely mixing the obtained vinasse lignocellulose according to a bath ratio of 9: 1, adding the mixture into a 13% sodium hydroxide solution for alkalization, wherein the alkalization temperature is 80 ℃, the alkalization time is 3 hours, the alkalized product is filtered by a 300-mesh stainless steel gauze, and the filtered product is prepared by mixing the following components in a bath ratio of 12: 1, transferring the mixed solution into a sodium sulfite/sodium hydroxide mixed solution for delignification, wherein the sodium sulfite/sodium hydroxide mixed solution comprises the following components in percentage by mass: 2.5 percent of sodium hydroxide, 2.5 percent of sodium sulfite and 95 percent of water, and the reaction condition is that the mixture is boiled for 3 hours at the temperature of 130 ℃. And finally adding 4% hydrogen peroxide for bleaching for 30 min.
(3) And (3) preparing the vinasse cellulose spinning solution, namely adding the prepared vinasse cellulose into an NMMO solvent with a refractive index of 1.42, dissolving for 3 hours at 95 ℃ under vacuum and reduced pressure, uniformly dissolving to obtain the spinning solution with the mass percentage concentration of 2%, and continuously placing for defoaming for later use.
(4) Preparing vinasse regenerated cellulose fiber, namely extruding vinasse cellulose solution into 150mm of air through capillary holes with the aperture of 1.2Then drawn to 10% NMMO/H 2 In the coagulation bath of O, the length of the coagulation bath is 900mm, the bath temperature is 40 ℃, the extrusion speed is 2.5m/min, and the total drawing multiple is 0.5 times. And solidifying, washing with water, drying and winding to obtain the vinasse regenerated cellulose fiber.
Compared with the traditional technology for preparing viscose fiber from wood pulp, the technology disclosed by the invention has the advantages that the cost of the used raw materials is reduced by 55%, the mechanical property of the fiber is 1.8cN/dtex, the hygroscopicity is 7.5%, and the antibacterial rate of escherichia coli is 95%.
Example 2
The embodiment provides a method for preparing green regenerated cellulose fibers by using vinasse as a raw material, which comprises the following steps:
(1) preparing the vinasse lignocellulose, namely soaking the beer vinasse in 0.1 percent sodium hydroxide solution by mass percent, wherein the soaking bath ratio is 16: 1, simultaneously carrying out mechanical stirring, wherein the dipping temperature is 35 ℃, the dipping time is 0.5h, and the stirring rotating speed is 200 RPM. Filtering with 300 mesh stainless steel gauze, repeatedly washing with water, filtering, drying at 50 deg.C for 3 hr, and sieving to obtain distiller's grains lignocellulose.
(2) Preparing the vinasse lignocellulose, namely mixing the obtained vinasse lignocellulose according to a bath ratio of 5:1, adding the mixture into 8% sodium hydroxide solution for alkalization, wherein the alkalization temperature is 60 ℃, the alkalization time is 2 hours, the alkalized product is filtered by a 300-mesh stainless steel gauze, and the filtered product is prepared by mixing the following components in a bath ratio of 15:1, transferring the mixed solution into a sodium sulfite/sodium hydroxide mixed solution for delignification, wherein the sodium sulfite/sodium hydroxide mixed solution comprises the following components in percentage by mass: 2% of sodium hydroxide, 2% of sodium sulfite and 96% of water, wherein the reaction condition is that the temperature is 100 ℃ and the boiling is carried out for 2 hours. And finally adding 2% hydrogen peroxide for bleaching for 30 min.
(3) And (3) preparing the vinasse cellulose spinning solution, namely adding the prepared vinasse cellulose into an NMMO solvent with a refractive index of 1.40, dissolving for 2 hours at 90 ℃ under vacuum and reduced pressure, uniformly dissolving to obtain the spinning solution with the mass percentage concentration of 1.5%, and continuously placing for defoaming for later use.
(4) Preparing vinasse regenerated cellulose fiber, namely extruding vinasse cellulose solution into a space of 100mm through a capillary hole with the aperture of 0.06mmIn the air, and then drawn to 5% NMMO/H 2 In the coagulation bath of O, the length of the coagulation bath is 900mm, the bath temperature is 35 ℃, the extrusion speed is 1m/min, and the total drawing multiple is 2.5 times. And solidifying, washing with water, drying and winding to obtain the vinasse regenerated cellulose fiber.
Compared with the traditional technology for preparing viscose fiber by wood pulp, the technology of the invention has the advantages that the cost of the used raw materials is reduced by 43 percent, the mechanical property of the fiber is 2.2cN/dtex, the hygroscopicity is 8 percent, and the antibacterial rate of escherichia coli is 97 percent.
Example 3
(1) Preparing the vinasse lignocellulose, namely soaking mixed vinasse with the beer vinasse/white spirit vinasse of 1/2 in 1 percent by mass of sodium hydroxide solution, wherein the soaking bath ratio is 18: 1, simultaneously carrying out mechanical stirring, wherein the dipping temperature is 60 ℃, the dipping time is 2h, and the stirring rotating speed is 800 RPM. Filtering with 300 mesh stainless steel gauze, repeatedly washing with water, filtering, drying at 85 deg.C for 8 hr, and sieving to obtain distiller's grains lignocellulose.
(2) Preparing the vinasse lignocellulose, namely mixing the obtained vinasse lignocellulose according to a bath ratio of 10: 1, adding the mixture into a 14% sodium hydroxide solution for alkalization, wherein the alkalization temperature is 90 ℃, the alkalization time is 4 hours, the alkalized product is filtered by a 300-mesh stainless steel gauze, and the filtered product is prepared by mixing the following components in a bath ratio of 15:1, transferring the mixed solution into a sodium sulfite/sodium hydroxide mixed solution for delignification, wherein the sodium sulfite/sodium hydroxide mixed solution comprises the following components in percentage by mass: 3% of sodium hydroxide, 5% of sodium sulfite and 92% of water, wherein the reaction condition is that the temperature is 150 ℃ and the boiling is carried out for 4 hours. And finally adding 5% sodium hypochlorite for bleaching for 30 min.
(3) And (3) preparing the vinasse cellulose spinning solution, namely adding the prepared vinasse cellulose into an NMMO solvent with a refractive index of 1.50, dissolving for 5 hours at 130 ℃ under vacuum and reduced pressure, obtaining a spinning solution with the mass percentage concentration of 3% after uniform dissolution, and continuously placing for defoaming for later use.
(4) Preparing vinasse regenerated cellulose fiber, namely extruding a vinasse cellulose solution into 200mm of air through pores with the diameter of 1.5mm, and then drawing to 14 percent NMMO/H 2 In the coagulation bath of O, the length of the coagulation bath is 900mm,the bath temperature is 50 ℃, the extrusion speed is 30m/min, and the total drawing multiple is 1 time. And solidifying, washing with water, drying and winding to obtain the vinasse regenerated cellulose fiber.
Compared with the traditional technology for preparing viscose fiber from wood pulp, the technology disclosed by the invention has the advantages that the cost of the used raw materials is reduced by 60%, the mechanical property of the fiber is 1.9cN/dtex, the hygroscopicity is 6.8%, and the antibacterial rate of escherichia coli is 98%.
FIG. 1 shows that: the appearance of the vinasse after brewing is obviously changed after the vinasse is treated by the technology, and the components are also converted into vinasse cellulose from vinasse lignocellulose.
FIG. 2 shows that: the prepared vinasse cellulose can obtain uniform spinning solution by the technology of the invention, and the vinasse cellulose fiber product is successfully prepared by the spinning technology.
Example 4
The embodiment provides a method for preparing green regenerated cellulose fibers by using vinasse as a raw material, which comprises the following steps:
(1) preparing vinasse lignocellulose, namely soaking beer vinasse in 0.15 percent sodium hydroxide solution by mass percent, wherein the soaking bath ratio is 14: 1, simultaneously carrying out mechanical stirring, wherein the dipping temperature is 40 ℃, the dipping time is 1.5h, and the stirring rotating speed is 350 RPM. And after the impregnation is finished, filtering by adopting a 300-mesh stainless steel gauze, repeatedly washing with water, filtering again, drying at 60 ℃ for 6 hours, and screening to obtain the vinasse lignocellulose.
(2) Preparing the vinasse lignocellulose, namely mixing the obtained vinasse lignocellulose according to a bath ratio of 7: 1, adding the mixture into a 12% sodium hydroxide solution for alkalization, wherein the alkalization temperature is 80 ℃, the alkalization time is 3 hours, the alkalized product is filtered by a 300-mesh stainless steel gauze, and the filtered product is prepared by mixing the following components in a bath ratio of 15:1, transferring the mixed solution into a sodium sulfite/sodium hydroxide mixed solution for delignification, wherein the sodium sulfite/sodium hydroxide mixed solution comprises the following components in percentage by mass: 2% of sodium hydroxide, 3% of sodium sulfite and 95% of water, wherein the reaction condition is that the temperature is 120 ℃ and the boiling is carried out for 3 hours. And finally adding 2% hydrogen peroxide for bleaching for 30 min.
(3) And (3) preparing the vinasse cellulose spinning solution, namely adding the prepared vinasse cellulose into an NMMO solvent with a refractive index of 1.43, dissolving for 2 hours at 90 ℃ under vacuum and reduced pressure, uniformly dissolving to obtain the spinning solution with the mass percentage concentration of 2%, and continuously placing for defoaming for later use.
(4) Preparing vinasse regenerated cellulose fiber, namely extruding vinasse cellulose solution into 150mm of air through pores with the pore diameter of 0.1mm, and then drawing to 20% NMMO/H 2 In the coagulation bath of O, the length of the coagulation bath is 900mm, the bath temperature is 30 ℃, the extrusion speed is 1.5m/min, and the total drawing multiple is 2.5 times. And solidifying, washing with water, drying and winding to obtain the vinasse regenerated cellulose fiber.
The prepared fiber has the mechanical property of 1.7 cN/dtex.
Example 5
The embodiment provides a method for preparing green regenerated cellulose fibers by using vinasse as a raw material, which comprises the following steps:
(1) preparing the vinasse lignocellulose, namely soaking the beer vinasse in 0.15 mass percent sodium hydroxide solution, wherein the soaking bath ratio is 14: 1, simultaneously carrying out mechanical stirring, wherein the dipping temperature is 40 ℃, the dipping time is 1.5h, and the stirring rotating speed is 350 RPM. And after the impregnation is finished, filtering by adopting a 300-mesh stainless steel gauze, repeatedly washing with water, filtering again, drying at 60 ℃ for 6 hours, and screening to obtain the vinasse lignocellulose.
(2) Preparing the vinasse lignocellulose, namely preparing the obtained vinasse lignocellulose according to a bath ratio of 7: 1, adding the mixture into a 12% sodium hydroxide solution for alkalization, wherein the alkalization temperature is 80 ℃, the alkalization time is 3 hours, the alkalized product is filtered by a 300-mesh stainless steel gauze, and the filtered product is prepared by mixing the following components in a bath ratio of 15:1 transferring the mixture into a sodium sulfite/sodium hydroxide mixed solution for delignification, wherein the sodium sulfite/sodium hydroxide mixed solution comprises the following components in percentage by mass: 2% of sodium hydroxide, 3% of sodium sulfite and 95% of water, wherein the reaction condition is that the temperature is 120 ℃ and the boiling is carried out for 3 hours. And finally adding 2% hydrogen peroxide for bleaching for 30 min.
(3) And (3) preparing the vinasse cellulose spinning solution, namely adding the prepared vinasse cellulose into an NMMO solvent with a refractive index of 1.43, dissolving for 2 hours at 90 ℃ under vacuum and reduced pressure, uniformly dissolving to obtain the spinning solution with the mass percentage concentration of 2%, and continuously placing for defoaming for later use.
(4) Preparing vinasse regenerated cellulose fiber, namely extruding a vinasse cellulose solution into 150mm of air through pores with the pore diameter of 0.1mm, and then drawing to 10% NMMO/H 2 In the coagulation bath of O, the length of the coagulation bath is 900mm, the bath temperature is 45 ℃, the extrusion speed is 1.5m/min, and the total drawing multiple is 2.5 times. And solidifying, washing with water, drying and winding to obtain the vinasse regenerated cellulose fiber.
The prepared fiber has the mechanical property of 2.2 cN/dtex.
Chinese patent CN201610424400.4 discloses a method for preparing regenerated cellulose fiber, which comprises the steps of pre-impregnating pulp in 50-65% of NMMO solvent, squeezing and crushing; adding the obtained mixture into 60-68% NMMO aqueous solution, adding antioxidant, and stirring and mixing uniformly; putting the obtained mixture into a vacuum environment, and obtaining a spinning solution at the temperature of 80-100 ℃; spinning the obtained spinning solution to obtain regenerated cellulose fibers, wherein a spinning bath is 15-20% of aqueous solution of NMMO (N-methyl-MO) during spinning, and the spinning temperature is 20-30 ℃.
Compared with the invention patent, the invention is different in that:
the pulp adopted by the invention is a high-grade raw material for preparing tencel fiber, has high cost and mostly depends on import. The raw material used by the invention is the vinasse which is the brewing waste, so that the domestic reserves are abundant, the price is low and the sources are wide. The production cost of the technology can be reduced by 27-35 percent when the same amount of regenerated cellulose fiber is prepared.
② compared with the comparison patent, the process is different in dipping process and spinning process. The reference patent is to impregnate the pulp raw material in NMMO solvent for the purpose of wetting and swelling the cellulose. The impregnation process before dissolution is to impregnate in 8-14% sodium hydroxide solution, the improvement of the process is beneficial to the separation and removal of non-cellulose components, the quality and quality of raw materials are improved, and the method can react with cellulose to generate alkalized cellulose and is more beneficial to and promotes the dissolution uniformity of spinning solution.
③ in the aspect of spinning technology, it is known that water is a poor solvent of NMMO/cellulose system, and the spinning solution will be precipitated and solidified into fiber when meeting the poor solvent. The higher the water content in the NMMO/water system, the faster the solidification, but the water content and temperature need to be matched to produce high quality fibers. In the comparison patent, the spinning bath is 15-20% aqueous solution of NMMO, and the spinning temperature is 20-30 ℃. The fiber is a low-water-content solidification bath solution and a low-temperature system, has a low solidification speed, is not suitable for high-speed spinning, and can not prepare high-quality precursor fibers because the adhesion and filament doubling phenomena among the fibers are caused by insufficient solidification of spinning trickle in the spinning process. The technology of the invention is 5-14% NMMO aqueous solution, the spinning temperature is 35-50 ℃, the water content in the coagulating bath is relatively high, the forming is facilitated, and the spinning temperature is matched. The optimal matching state for fiber forming and structure regulation can be achieved. As shown in FIG. 3, the fibers formed according to the system of the invention at 30 ℃ in 20% aqueous NMMO solution (example 4) have a porous structure inside, resulting in a lower fiber strength of only 1.7cN/dtex, while the fibers formed at 45 ℃ in 10% aqueous NMMO solution (example 5) have a tighter structure inside and a fiber strength of up to 2.2 cN/dtex. It can be seen that the technology of the present invention has obvious advancement.
In the aspect of delignification, Chinese patent CN113499760A takes wood as a raw material, adopts sodium sulfite/sodium hydroxide mixed solution to heat for 6-12 hours at 80-100 ℃ to remove hemicellulose and lignin, and then uses dimethyl siloxane to process and prepare hydrophobic wood. Compared with the technology, the cellulose in the vinasse is mostly the fruit shell of the grain, the structure is more compact, and the cellulose content is higher. Spinning is a high-standard material preparation method, the requirements on the cellulose content and purity of stock solution are very high, and incomplete removal of impurities such as lignin and the like easily causes the spinning solution to contain impurities, so that the spinning fails. The vinasse cellulose prepared by delignifying vinasse by using a patent report technology cannot be completely dissolved and cannot meet the spinning requirement. Therefore, the technology of the invention is improved, a concentrated alkali alkalization process step is added before the sodium sulfite/alkali liquor is used for removing lignin, and a sodium sulfite/sodium hydroxide lignin removal process is improved. Through the technical innovation, the vinasse cellulose can be completely dissolved to form a spinning solution for smooth spinning, and the spinning solution is shown in figures 1-2. The delignification process of the technology of the invention comprises the steps of soaking 8-14% concentrated alkali for 2-4h at the temperature of 60-90 ℃, wherein the bath liquid ratio is 5-10: 1, after the impregnation, treating the mixture for 2 to 4 hours in a mixed system of 2 to 3 percent of sodium hydroxide, 2 to 5 percent of sodium sulfite and 92 to 98 percent of water at the temperature of 100 ℃ and 150 ℃. The cellulose content treated by the technology of the invention reaches more than 99 percent, and the cellulose can be smoothly dissolved and spun. The method can dissolve the vinasse lignocellulose in NMMO in one step by treating and purifying the vinasse lignocellulose, and has the advantages of shortened process and simpler operation. Therefore, the lignin removal process has obvious advancement.
The invention is a technology for changing waste into valuable, takes the waste vinasse as the raw material, firstly proposes the waste vinasse as the fiber preparation raw material and develops a process chain preparation technology for preparing the vinasse cellulose fiber by taking the vinasse as the raw material, opens up the way of high-value utilization of the vinasse waste, greatly reduces the production cost of the cellulose (reduces the cost by 43-60 percent), and simultaneously solves the problem of environmental pollution caused by vinasse stacking treatment.
Claims (10)
1. A method for preparing regenerated cellulose fiber by using vinasse as a raw material comprises the following steps:
(1) soaking the vinasse after brewing in dilute alkali liquor, filtering, washing with water, drying, and separating to obtain vinasse lignocellulose;
(2) crushing the vinasse lignocellulose obtained in the step (1), alkalizing by using alkali liquor, performing a lignin removal process, washing with water, filtering, and drying to obtain the vinasse cellulose;
(3) and (3) dissolving the vinasse cellulose in the step (2) in a solvent, and spinning the obtained vinasse cellulose spinning solution to obtain the regenerated cellulose fiber.
2. The method according to claim 1, wherein the distiller's grains in the step (1) are one of distiller's grains of white spirit, distiller's grains of beer, and distiller's grains of beer/distiller's grains of white spirit; the dilute alkali solution is: sodium hydroxide solution with mass percent concentration of 0.1-1%.
3. The method as claimed in claim 1, wherein the impregnation in step (1) is dynamic stirring impregnation, the stirring rotation speed is 200-800RPM, the impregnation temperature is 35-60 ℃, the impregnation time is 0.5-2h, and the impregnation bath ratio is 12-18: 1; the filtration and separation are carried out by gauze treatment.
4. The method according to claim 1, wherein the quality fraction of the alkali liquor in the step (2) is 8-14%; the alkalization temperature is 60-90 ℃, the alkalization time is 2-4h, and the alkalization bath ratio is 5-10: 1.
5. the method according to claim 1, wherein the delignification process in the step (2) is: adding the alkalized vinasse lignocellulose into a sodium sulfite/sodium hydroxide mixed solution for boiling, wherein the bath ratio is 10-15:1, and the sodium sulfite/sodium hydroxide mixed solution comprises the following components in percentage by mass: 2-3% of sodium hydroxide, 2-5% of sodium sulfite and 92-98% of water; the boiling temperature is 100-; bleaching with hydrogen peroxide or sodium hypochlorite after the delignification process is finished.
6. The method of claim 1, wherein the solvent in step (3) comprises one of a conventional base/urea system, an N-methylmorpholine-N-oxide NMMO system, an ionic liquid system; the mass percentage of the vinasse cellulose in the vinasse cellulose spinning solution is 1.5-3%; the spinning is wet spinning or dry-jet wet spinning.
7. The method according to claim 6, characterized in that the solvent is a N-methylmorpholine-N-oxide NMMO system; the refractive index of the N-methylmorpholine-N-oxide NMMO system is 1.40-1.50; the dissolution conditions were: dissolving at 90-130 deg.C under vacuum and reduced pressure for 2-5 h.
8. The method of claim 6, wherein the spinning is dry-jet wet spinning; the dry-jet wet spinning process parameters are as follows: warp beamThe spinning solution stream extruded through the capillary holes firstly passes through air and then enters the coagulating bath solution for coagulation, wherein the distance of the air section is 100-200mm, the extrusion speed is 1-30m/min, the pore diameter of the capillary holes is 0.06-1.5mm, the temperature of the coagulating bath solution is 35-50 ℃, and the composition of the coagulating bath solution is 5-14% of NMMO/H 2 O system, total draft multiple is 0.5-2.5 times.
9. A regenerated cellulose fiber produced by the method of claim 1.
10. Use of regenerated cellulose fibres prepared according to the process of claim 1 in textiles.
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