CN117364521A - Method for efficiently and gradient pulping, recycling and functional fiber preparation of waste cotton textiles - Google Patents
Method for efficiently and gradient pulping, recycling and functional fiber preparation of waste cotton textiles Download PDFInfo
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- CN117364521A CN117364521A CN202311248885.2A CN202311248885A CN117364521A CN 117364521 A CN117364521 A CN 117364521A CN 202311248885 A CN202311248885 A CN 202311248885A CN 117364521 A CN117364521 A CN 117364521A
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- 229920000742 Cotton Polymers 0.000 title claims abstract description 87
- 239000000835 fiber Substances 0.000 title claims abstract description 54
- 239000004753 textile Substances 0.000 title claims abstract description 48
- 239000002699 waste material Substances 0.000 title claims abstract description 48
- 238000004537 pulping Methods 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000004064 recycling Methods 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229920002678 cellulose Polymers 0.000 claims abstract description 25
- 239000001913 cellulose Substances 0.000 claims abstract description 25
- 238000000227 grinding Methods 0.000 claims abstract description 16
- 239000004744 fabric Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000004061 bleaching Methods 0.000 claims abstract description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 17
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 14
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 claims description 12
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 10
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 10
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 10
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 9
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 7
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 5
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 5
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 4
- 238000007385 chemical modification Methods 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 2
- 239000012634 fragment Substances 0.000 claims 1
- 238000005470 impregnation Methods 0.000 claims 1
- 238000003801 milling Methods 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 239000002002 slurry Substances 0.000 claims 1
- 238000010009 beating Methods 0.000 abstract description 14
- 238000002791 soaking Methods 0.000 abstract description 7
- 230000009471 action Effects 0.000 abstract description 5
- 230000008859 change Effects 0.000 abstract description 3
- 238000007639 printing Methods 0.000 abstract description 3
- 238000004043 dyeing Methods 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract description 2
- 239000013043 chemical agent Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 238000007670 refining Methods 0.000 description 18
- 239000000243 solution Substances 0.000 description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000010784 textile waste Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000004042 decolorization Methods 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- -1 p-toluenesulfonyl group Chemical group 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
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- 239000012466 permeate Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 238000009897 hydrogen peroxide bleaching Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21D—TREATMENT OF THE MATERIALS BEFORE PASSING TO THE PAPER-MAKING MACHINE
- D21D1/00—Methods of beating or refining; Beaters of the Hollander type
- D21D1/20—Methods of refining
- D21D1/30—Disc mills
-
- 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
-
- 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
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/10—Bleaching ; Apparatus therefor
- D21C9/16—Bleaching ; Apparatus therefor with per compounds
- D21C9/163—Bleaching ; Apparatus therefor with per compounds with peroxides
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21D—TREATMENT OF THE MATERIALS BEFORE PASSING TO THE PAPER-MAKING MACHINE
- D21D1/00—Methods of beating or refining; Beaters of the Hollander type
- D21D1/02—Methods of beating; Beaters of the Hollander type
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Paper (AREA)
Abstract
The invention discloses a method for efficiently and gradient pulping, recycling and functional fiber preparation of waste cotton textiles, and belongs to the field of textile printing and dyeing processing. And after the waste cotton textiles are cut, carrying out gradient grinding treatment and bleaching on the cut cloth pieces by a chemical agent pre-soaking, a disc mill and a watt beating machine to obtain cotton pulp fibers prepared by taking the waste cotton textiles as raw materials. The invention makes the fiber generate a certain amount of physical change under the action of various mechanical forces generated by the pulping machine, so that the fiber is further thinned, swelled, rubbed and crushed, and single fiber fuzzing is promoted. Further bleaching to remove impurities such as color and the like to achieve the whiteness of the fiber. The hydrogen bonding force between fibers can be increased by pulping, the strength and softness of paper sheets can be improved, and the requirements of normal papermaking are met. Meanwhile, the high-quality cellulose obtained after treatment can be further chemically modified to prepare the functionalized cellulose, so that more reuse directions of the cellulose are provided.
Description
Technical Field
The invention belongs to the field of textile printing and dyeing processing, and particularly relates to a method for efficiently and gradient pulping, recycling and functional fiber preparation of waste cotton textiles.
Background
With the improvement of economic level and living standard of people, the consumption of people to clothing is rapidly improved, so that the service cycle of textiles is shortened, and a large amount of textile waste is wasted. These wastes not only waste resources but also cause environmental pollution. For the treatment of textile waste, methods such as stacking, landfill, incineration and the like are basically adopted in the past, but the disadvantage is that the stacking of the textile waste occupies land and is easy to collapse; the accumulated waste is exposed in the air, and dust and impurities are accumulated, so that the environmental sanitation is affected; under the action of rainwater, dyes and other harmful components on the textile waste are leached out and permeate into the ground to pollute the underground water. The landfill is carried out under the ground surface, and although the ground environment is not affected, the landfill treated field is hardly reused in the city and has an additional cost; because of the nondegradability of chemical fibers, particularly synthetic fibers, the landfill of chemical fiber waste can harden soil; also, harmful substances on the waste material may permeate into soil with water, penetrate into the ground, and contaminate the soil and groundwater. The incineration of waste fabrics generates a large amount of dust and harmful gas to pollute the atmosphere, so that the environmental sanitation is affected, and the incinerated chemical fiber residues are not easy to treat. Therefore, the recycling of waste textiles is a key concern.
China is the first major textile country worldwide, and the total amount of textile fiber processing accounts for more than 50% of the world. Cotton fiber has the characteristics of good moisture absorption and air permeability, excellent hand feeling, strength and the like, and is popular with people. With the continuous increase of the consumption of fiber per person, a large amount of waste textiles are produced annually in China. The recycling of waste textiles has important significance for saving resources, reducing pollution and reducing carbon, is an important measure for effectively supplementing raw material supply of textile industry in China and relieving resource environment constraint, and is an important content for establishing a sound green low-carbon recycling development economic system. In the process of recycling waste cotton textiles, the color of the waste cotton textiles can influence the subsequent use of the waste cotton textiles. Thus, it is desirable to avoid subjecting cellulose to pulping processes with excessive degradation.
Cotton pulp has wide application in various fields, and the main raw materials for preparing the cotton pulp at present are from waste cotton, cotton linters and the like in the textile industry. These pulps are relatively pure in cellulose and the fibers are elongated and elastic, tough and resistant to folding and have good absorbency. The paper is fine and soft, has high opacity, and can be stored for a long time. The method is used for manufacturing articles with high paper money value; unbleached cotton pulp is used for manufacturing vulcanized fiber base paper and the like; the bleached cotton pulp is mainly used for manufacturing high-grade printing paper such as filter paper, liquid absorbing base paper, drawing paper, bond paper, paper currency and the like. Because the cellulose content in the cotton pulp is very high, the cotton pulp can also be used as raw materials of derivatives such as rayon, cellulose acetate, nitrocellulose, carboxymethyl cellulose and the like.
In conventional pulping and papermaking, the pulp, which is not subjected to disc mill and watt beater grinding after washing, bleaching and purifying, contains a plurality of fiber bundles. Because the fiber is too thick and long, the surface is smooth, stiff and elastic, the specific surface area of the fiber is small, and the bonding performance is lacking. If the unground paper pulp is directly used for papermaking, the paper is difficult to uniformly distribute on a net, the formed paper is loose and porous, the surface is rough and easy to fluff, the bonding strength is very low, the paper performance is very poor, and the use requirement cannot be met. Therefore, the pulping process needs to be designed according to the characteristics of the waste cotton textile raw materials; there is a need to develop a method for preparing cotton pulp aiming at the raw material characteristics of waste cotton textiles and a method for preparing functional cellulose by further chemical modification of the recovered cellulose.
Disclosure of Invention
The invention aims to overcome the problems of too thick and long fiber, small specific surface area, lack of binding energy and the like in the traditional cotton pulp preparation process aiming at the defects of the existing recycling technology of waste cotton textiles.
The invention provides a novel method for preparing functional cellulose by using a pulping machine and a watt pulping machine to obtain high-quality cotton pulp through different gradient pulping on the basis of taking clean cooking auxiliary agents such as hydrogen peroxide, sodium hexametaphosphate and benzoquinone as the cooking auxiliary agents and further chemically modifying the high-quality cotton pulp.
In order to achieve the aim, the invention provides a method for preparing cotton pulp by auxiliary waste cotton textile gradient pulping by compounding penetration auxiliary agents such as magnesium sulfate, sodium hexametaphosphate and the like, which comprises the following main steps of:
(1) Dispersing cotton pulp obtained by stewing and decoloring waste cotton textiles in an aqueous solution system containing magnesium sulfate, sodium hexametaphosphate and benzoquinone to obtain a mixed system, and fully soaking for 30-60min. Filtering the immersed cloth with a sieve, taking out, draining water, grinding the cloth with a tile Li Dajiang machine, a disc grinding grinder and the like, filtering with a screen, collecting, bleaching and airing the ground cotton fibers, and obtaining the high-quality cotton pulp prepared from waste cotton textiles. Dispersing the high-quality cotton pulp obtained by treatment in DMAC, and fully activating. Adding a proper amount of anhydrous lithium chloride, fully stirring, cooling to 8 ℃ after the fiber is thoroughly dissolved, adding a mixture of DMAC and triethylamine, then dropwise adding a DMAC solution dissolved with paratoluenesulfonyl chloride, and stirring at 8 ℃ for 24 hours to obtain Tscell. The obtained TsCell is dissolved in DMSO, ethylenediamine is added into the system and stirred for 6 hours, the product is precipitated in acetone, and the NCell is obtained by washing and drying with ethanol.
Further, in the step (1), the magnesium sulfate accounts for 0.5-10% of the mass of the waste cotton textile in percentage by weight.
Further, in the step (1), the sodium hexametaphosphate accounts for 0.01-5% of the mass of the waste cotton textile in percentage by weight.
Further, in the step (1), the solid-to-liquid ratio of the mixed system is 1:4-20.
Further, in the step (1), when gradient grinding is performed: the disc refining slits are respectively 2.0mm, 0.5mm and 0.1mm; the tile Li Dajiang machine pulps for 3min, 10min and 15min respectively. The tile Li Dajiang machine and the refiner are sequentially and continuously processed for 2-20 minutes.
Further, the step (1) further comprises the step of bleaching the pulp ground by the pulping machine and the watt pulping machine by hydrogen peroxide, wherein the hydrogen peroxide accounts for 2-10% of the mass of the waste cotton textiles, the treatment temperature is 60-90 ℃, and the time is 60 minutes.
Further, in the step (1), the solid-to-liquid ratio of the mixed system during hydrogen peroxide bleaching is 1:4-20.
Further, in the step (1), the molar ratio of the cellulose glucose unit to the p-toluenesulfonyl chloride is 1:1-2.
Further, the mass-volume ratio of the lithium chloride to the high-quality cotton pulp in the step (1) is 1mL/1g; the mass ratio of the triethylamine to the high-quality cotton pulp is 2:1; the molar ratio of ethylenediamine to TsCell was 25:1.
Further, the reaction temperature in the step (1) is 100 ℃ and the time is 6 hours.
Advantageous effects
The invention discloses a method for efficiently and gradiently pulping, recycling and preparing functional fibers of waste cotton textiles, which has at least the following beneficial effects compared with the prior art:
(1) The invention discloses a high-efficiency gradient pulping recycling method for waste cotton textiles and a method for preparing functional fibers, which can enable the fibers to undergo a certain amount of physical change under the mechanical action of a disc mill and a tile beating machine so as to further refine, swell, rub and crush the fibers and promote the single fibers to fuzz (the surface area of the fibers is enlarged);
(2) The invention can increase the hydrogen bonding force between fibers through pulping, improve the strength and softness of paper sheets and meet the requirements of normal papermaking;
(3) The invention can adjust the specific pressure of the pulp according to the process requirements of pulp grinding raw materials and pulp grinding quality, and simultaneously takes account of the cutting of the fiber and the internal grinding of the fiber, so that the fiber is divided into filaments and is broomed, thereby playing the roles of stabilizing the quality of high-concentration pulp grinding and saving energy;
(4) The product obtained by the invention is close to the performance requirement of the traditional pulping product, reduces pulping energy consumption, and is beneficial to the development of the subsequent recycling process of pulping waste cotton textiles and the like.
(5) The functional cellulose obtained by the invention can be further synthesized with other products, and is beneficial to reutilization of waste cotton textiles.
Drawings
Fig. 1 is a treatment flow of a waste cotton textile regeneration pulping process.
FIG. 2 shows the effect of different refining modes on fiber morphology; (a) beating for 30 min by a tile Li Dajiang machine; (b, c) influence on cotton fiber morphology when the refining pitch of the refiner is 2 mm and 1mm respectively; (d) Fiber state under an optical microscope after pulping for 30 min by a tile Li Dajiang machine; (e-f) fiber state under an optical microscope when the refining pitch of the refiner is 2 mm and 1mm respectively; (g-i) white light photographs of air-dried pulp after different refining modes.
FIG. 3 is a microscope image of the effect of different refining slits and beating times on fiber morphology, (a-c) disc refining slits 2.0mm, 0.5mm, 0.1mm, respectively; (d-f) the beating time of the tile Li Dajiang machine is 3min, 10min and 15min respectively.
FIG. 4 is an SEM image of the effect of different refining slits and beating times on fiber morphology, with (a-c) disc refining slits of 2.0mm, 0.5mm, 0.1mm, respectively; (d-f) the beating time of the tile Li Dajiang machine is 3min, 10min and 15min respectively.
Fig. 5 is a diagram of a process for preparing regenerated cotton pulp functional fiber.
Fig. 6 is a TsCell infrared spectrum.
Fig. 7 is an NCell infrared spectrum.
Detailed Description
Hereinafter, the present invention will be described in detail. Before the description, it is to be understood that the terms used in this specification and the appended claims should not be construed as limited to general and dictionary meanings, but interpreted based on the meanings and concepts corresponding to technical aspects of the present invention on the basis of the principle that the inventor is allowed to define terms appropriately for the best explanation. Accordingly, the description set forth herein is merely a preferred example for the purpose of illustration and is not intended to limit the scope of the invention, so that it should be understood that other equivalents or modifications may be made thereto without departing from the spirit and scope of the invention.
The outstanding advantages and salient features of the invention are further illustrated by way of the following examples, which are by no means limiting. Those skilled in the art will appreciate that modifications may be made to the invention without departing from its spirit or scope. Unless otherwise indicated, the reagents and apparatus used in the examples below are commercially available products.
The basic route of the invention is as follows: washing and airing the waste cotton textiles, and removing accessories such as buttons, zippers and the like; cut into pieces of 5 cm ×5 cm size, placed in self-sealing bags overnight (equilibrated for moisture), and tested for moisture content. Weighing waste cotton textile cloth 0.5-kg with absolute dry weight for standby; sodium hydroxide solution 30/g/L was prepared for use. Soaking the cloth piece with 5-10 times of water, adding hydrogen peroxide 0.2-10%, sodium hexametaphosphate 0.01-5%, benzoquinone 0.01-0.5%, and soaking for 30-60min. Then adding sodium hydroxide to 20-60 g/L, fixing the volume to 5L, transferring to a pressure-resistant digestion reactor, and preserving the temperature for 0.5-3h. Diluting with water, washing, and filtering with a sieve. Further grinding with a grinder to obtain high-quality cotton pulp. High quality cotton pulp (1.0 g) was dispersed in DMAC and fully activated at 160℃and cooled to 100℃and a suitable amount of anhydrous lithium chloride (2.0 g) was added. After cooling to room temperature after sufficient stirring and after the high-quality cotton pulp was completely dissolved, the cellulose solution was cooled to 8℃and a mixture of DMAC (2.1 ml) and triethylamine (3 ml) was added thereto, and then a DMAC solution in which p-toluenesulfonyl chloride (2.118 g) was dissolved was added dropwise. Stirred at 8℃for 24 hours. The product was poured into 150ml ice water and precipitated and filtered to give TsCell (cellulose p-benzenesulfonate). TsCell (1.0 g) was dissolved in DMSO solution, and 25-fold molar amount of ethylenediamine was added to the system and stirred at 100℃for 6 hours, and cooled to room temperature. The product was precipitated in acetone and subsequently washed with ethanol and dried to give NCell (amino cellulose).
Example 1
Weighing waste cotton textile cloth 0.5-kg, placing in 2L water solution containing 2% hydrogen peroxide, 0.1% benzoquinone and 1% sodium hexametaphosphate, and soaking for half an hour. Then adding sodium hydroxide to 30g/L, adding sodium hydroxide to 30g/L, fixing the volume to 5L, transferring into a high-pressure reaction kettle, heating the high-pressure reaction kettle to 160 ℃ at a heating rate of 4-6 ℃/min under the rotating condition, and maintaining for 3 hours, so as to perform oxidation decolorization and degradation reaction of cotton fibers. After the reaction is finished, the electric heater and the rotary switch are turned off, and after the reaction kettle is cooled to room temperature, the reaction kettle is opened, and the reaction product is taken out. Filtering the reaction product by a screen to obtain a cotton pulp fiber aggregate, vacuumizing and filtering the residual mixed solution by a filter membrane to obtain cotton pulp fibers, and enabling the cotton pulp aggregate to be a reusable fiber raw material by the mechanical action of a pulping machine and a watt pulping machine. Gradient grinding: the tile Li Dajiang machine and the refiner are sequentially and continuously processed. The disc mill pulping slits are 2.0mm, 0.5mm and 0.1mm in sequence, and the treatment is carried out for 5min; the Wallich beater sequentially beaters for 3min, 10min and 15min.
Example 2
Weighing waste cotton textile cloth 0.5. 0.5 kg, placing in 5L water solution containing 1% hydrogen peroxide, 0.5% benzoquinone and sodium hexametaphosphate with content of 2%, and soaking for half an hour. Then adding sodium hydroxide to 40 g/L, fixing the volume to 5L, transferring into a high-pressure reaction kettle, heating the high-pressure reaction kettle to 160 ℃ at a heating rate of 4-6 ℃/min under the rotating condition, and maintaining for 140min to perform oxidation decolorization and degradation reaction of cotton fibers. After the reaction is finished, the electric heater and the rotary switch are turned off, and after the reaction kettle is cooled to room temperature, the reaction kettle is opened, and the reaction product is taken out. The reaction product is filtered by a screen to obtain a cotton pulp fiber aggregate, and the cotton pulp aggregate is mechanically acted by a pulping machine and a watt pulping machine to become a reusable fiber raw material. Gradient grinding: the tile Li Dajiang machine and the refiner are sequentially and continuously processed. The disc mill pulping slits are 2.0mm, 0.5mm and 0.1mm in sequence, and the treatment is carried out for 2min; the Wallich beater sequentially beaters for 3min, 10min and 15min.
Example 3
Weighing waste cotton textile cloth 0.5. 0.5 kg, placing in 5L water solution containing 1% hydrogen peroxide, 0.5% benzoquinone and 3% sodium hexametaphosphate, and soaking for half an hour. Then adding sodium hydroxide to 50 g/L, fixing the volume to 5L, transferring into a high-pressure reaction kettle, heating the high-pressure reaction kettle to 160 ℃ at a heating rate of 4-6 ℃/min under the rotating condition, and maintaining for 180min to perform oxidation decolorization and degradation reaction of cotton fibers. And after the reaction is finished, closing and rotating the switch, opening the reaction kettle after the reaction kettle is cooled to the room temperature, and taking out a reaction product. Filtering the reaction product by a screen to obtain a cotton pulp fiber aggregate, and enabling the cotton pulp aggregate to be a reusable fiber raw material by the mechanical action of a pulping machine and a tile electric heating pulping machine. Gradient grinding: the tile Li Dajiang machine and the refiner are sequentially and continuously processed. The disc mill pulping slits are 2.0mm, 0.5mm and 0.1mm in sequence, and the treatment is carried out for 10min; the Wallich beater sequentially beaters for 3min, 10min and 15min.
High quality cotton pulp (1.0 g) was dispersed in DMAC and fully activated at 160℃and cooled to 100℃and a suitable amount of anhydrous lithium chloride (2.0 g) was added. After cooling to room temperature after sufficient stirring and after the high-quality cotton pulp was completely dissolved, the cellulose solution was cooled to 8℃and a mixture of DMAC (2.1 ml) and triethylamine (3 ml) was added thereto, and then a DMAC solution in which p-toluenesulfonyl chloride (2.118 g) was dissolved was added dropwise. Stirred at 8℃for 24 hours. The product was poured into 150ml ice water and precipitated and filtered to give TsCell (cellulose p-benzenesulfonate). TsCell (1.0 g) was dissolved in DMSO solution, and 25-fold molar amount of ethylenediamine was added to the system and stirred at 100℃for 6 hours, and cooled to room temperature. The product was precipitated in acetone and subsequently washed with ethanol and dried to give NCell (amino cellulose).
Fig. 1 shows a treatment flow of a waste cotton textile regeneration pulping process. Firstly, waste textiles are pretreated, and the fibers are bleached through gradient pulping treatment, so that high-quality fibers are obtained.
FIG. 2 shows the effect of different refining modes on the morphology of the fibers, respectively beating and refining by a watt beater and a refiner, and then observing the morphology change of the cotton fibers under a microscope; (a) beating for 30 min by a tile Li Dajiang machine; (b, c) influence on cotton fiber morphology when the refining pitch of the refiner is 2 mm and 1mm respectively; (d) Fiber state under an optical microscope after pulping for 30 min by a tile Li Dajiang machine; (e-f) fiber state under an optical microscope when the refining pitch of the refiner is 2 mm and 1mm respectively; (g-i) white light photographs of air-dried pulp after different refining modes.
Fig. 3 is a microscope image of the effect of different refining slits and beating times on fiber morphology, refining the cooked cotton pulp under the conditions that the slits are 2.0mm, 0.5mm and 0.1mm respectively, then beating for 3min, 10min and 15min respectively by a tile Li Dajiang machine, and finally observing the pulp under a microscope. (a-c) disc refiner slits of 2.0mm, 0.5mm, 0.1mm, respectively; (d-f) the beating time of the tile Li Dajiang machine is 3min, 10min and 15min respectively.
FIG. 4 is an SEM image of the effect of different refining slits and beating times on fiber morphology, with (a-c) disc refining slits of 2.0mm, 0.5mm, 0.1mm, respectively; (d-f) the beating time of the tile Li Dajiang machine is 3min, 10min and 15min respectively.
FIG. 5 shows a process for preparing regenerated cotton pulp functional fiber, dispersing high quality cotton pulp (1.0 g) in DMAC, fully activating at 160 ℃, cooling to 100 ℃, and adding a proper amount of anhydrous lithium chloride (2.0 g). After cooling to room temperature after sufficient stirring and after the high-quality cotton pulp was completely dissolved, the cellulose solution was cooled to 8℃and a mixture of DMAC (2.1 ml) and triethylamine (3 ml) was added thereto, and then a DMAC solution in which p-toluenesulfonyl chloride (2.118 g) was dissolved was added dropwise. Stirred at 8℃for 24 hours. The product was poured into 150ml ice water and precipitated and filtered to give TsCell. TsCell (1.0 g) was dissolved in DMSO solution, and 25-fold molar amount of ethylenediamine was added to the system and stirred at 100℃for 6 hours, and cooled to room temperature. The product was precipitated in acetone and subsequently washed with ethanol and dried to give NCell.
Fig. 6 is a TsCell infrared spectrum, γ=2900 cm -1 For CH connected to hydroxy 2 The symmetrical stretching vibration peak is known from the TsCell curve that TsCell is significantly attenuated and broadened at this point, and at γ=1362 cm -1 And 1174 cm -1 The appearance of a new peak, which is SO 2 Is not shown in the figure). At γ=1597 cm -1 、1500 cm -1 And 1456 cm -1 The new peak appearing here is the C peak of the benzene ring in the p-toluenesulfonyl group, indicating that the-OH moiety of cellulose is replaced by p-toluenesulfonyl.
Fig. 7 is an infrared spectrum of the NCell, where the NCell is at γ=1320 cm -1 SO at 2 The absorption peak is weakened, and gamma=3500-3000 cm -1 There is a new absorption peak, which is the absorption peak of primary amine. At the same time, γ=812 cm -1 The characteristic absorption peak of cellulose p-toluenesulfonate is obviously weakened, and NH is judged 2 Substituted p-toluenesulfonyl.
Claims (10)
1. The preparation method of the efficient gradient pulping recycling and functional fiber of the waste cotton textiles is characterized by comprising the following steps of:
(1) Washing and airing waste cotton textiles, and dividing the waste cotton textiles into fragments;
(2) Dispersing the cloth into an aqueous solution system containing magnesium sulfate, benzoquinone, sodium hexametaphosphate and hydrogen peroxide to obtain a mixed system, and carrying out gradient grinding slurry treatment on the cloth through pre-impregnation gradient grinding;
(3) Filtering with a screen, collecting, bleaching, washing and airing the cotton fibers subjected to pulp grinding to obtain high-quality cotton pulp prepared by taking waste cotton textiles as raw materials;
(4) And carrying out chemical modification on the high-quality cotton pulp to obtain the functional cellulose.
2. The preparation method of claim 1, wherein the magnesium sulfate accounts for 0.5-10% of the mass of the waste cotton textile in percentage by weight.
3. The preparation method of claim 1, wherein the sodium hexametaphosphate is used in an amount of 0.01-5% by weight of the waste cotton textile.
4. The preparation method of claim 1, wherein the hydrogen peroxide is used in an amount of 0.01-5% by weight of the waste cotton textile.
5. The method according to claim 1, wherein during gradient milling: the pulping slits of the pulping machine are respectively 2.0mm, 0.5mm and 0.1mm; the tile Li Dajiang machine pulps for 3min, 10min and 15min respectively, and the refiner and the tile force pulper process for 2-20min in sequence.
6. The method according to claim 1, wherein the bleaching process comprises hydrogen peroxide in an amount ranging from 2 to 10% by weight of the waste cotton textile.
7. The method of claim 1, wherein the chemical modification is that cotton pulp is dispersed in DMF, after adding lithium chloride, adding triethylamine, then adding p-toluenesulfonyl chloride dropwise, stirring at 8 ℃ to obtain cellulose p-benzenesulfonate, and then adding ethylenediamine to react to obtain the amino cellulose.
8. The method of claim 7, wherein the molar ratio of the cellulose glucose units to the para-toluenesulfonyl chloride is 1:1-2.
9. The method of claim 7, wherein the mass to volume ratio of lithium chloride to high quality cotton pulp is 1mL/1g; the mass ratio of the triethylamine to the high-quality cotton pulp is 2:1; the molar ratio of ethylenediamine to cellulose p-benzenesulfonate was 25:1.
10. The method according to claim 7, wherein the temperature during the reaction is 100 ℃ and the reaction time is 6 hours.
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