CN112251832B - Preparation method of regenerated protein composite cellulose fiber - Google Patents
Preparation method of regenerated protein composite cellulose fiber Download PDFInfo
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- CN112251832B CN112251832B CN202011026373.8A CN202011026373A CN112251832B CN 112251832 B CN112251832 B CN 112251832B CN 202011026373 A CN202011026373 A CN 202011026373A CN 112251832 B CN112251832 B CN 112251832B
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- 102000004169 proteins and genes Human genes 0.000 title claims abstract description 128
- 108090000623 proteins and genes Proteins 0.000 title claims abstract description 128
- 229920003043 Cellulose fiber Polymers 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002131 composite material Substances 0.000 title claims abstract description 16
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical class O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 78
- 238000009987 spinning Methods 0.000 claims abstract description 51
- 239000000843 powder Substances 0.000 claims abstract description 32
- 239000000243 solution Substances 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 229910021536 Zeolite Inorganic materials 0.000 claims description 65
- 239000010457 zeolite Substances 0.000 claims description 65
- 239000007788 liquid Substances 0.000 claims description 31
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- 102000035118 modified proteins Human genes 0.000 claims description 24
- 108091005573 modified proteins Proteins 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 230000004913 activation Effects 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003292 glue Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 230000001112 coagulating effect Effects 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- 150000003973 alkyl amines Chemical class 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- -1 polyoxyethylene Polymers 0.000 claims description 6
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 6
- 235000011152 sodium sulphate Nutrition 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000000835 fiber Substances 0.000 abstract description 33
- 238000000034 method Methods 0.000 abstract description 25
- 238000001914 filtration Methods 0.000 abstract description 14
- 230000008569 process Effects 0.000 abstract description 14
- 229920000297 Rayon Polymers 0.000 abstract description 13
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 8
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 6
- 239000003513 alkali Substances 0.000 abstract description 5
- 238000006359 acetalization reaction Methods 0.000 abstract description 4
- 150000001844 chromium Chemical class 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- 230000008961 swelling Effects 0.000 abstract description 4
- 238000007711 solidification Methods 0.000 abstract description 3
- 230000008023 solidification Effects 0.000 abstract description 3
- 238000007670 refining Methods 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract 1
- 235000018102 proteins Nutrition 0.000 description 108
- 238000005406 washing Methods 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 10
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 10
- 229920002678 cellulose Polymers 0.000 description 9
- 239000001913 cellulose Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- 241000255789 Bombyx mori Species 0.000 description 7
- 108010073771 Soybean Proteins Proteins 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 235000019710 soybean protein Nutrition 0.000 description 7
- 241000382353 Pupa Species 0.000 description 6
- 235000021120 animal protein Nutrition 0.000 description 6
- 238000006477 desulfuration reaction Methods 0.000 description 6
- 230000023556 desulfurization Effects 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 238000012216 screening Methods 0.000 description 5
- 235000010265 sodium sulphite Nutrition 0.000 description 5
- 210000002268 wool Anatomy 0.000 description 5
- 238000004383 yellowing Methods 0.000 description 5
- 108010064851 Plant Proteins Proteins 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 235000021118 plant-derived protein Nutrition 0.000 description 4
- 241001465754 Metazoa Species 0.000 description 3
- 229920006297 regenerated protein fiber Polymers 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 229920002494 Zein Polymers 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000001066 destructive effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 210000003746 feather Anatomy 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000005019 zein Substances 0.000 description 2
- 229940093612 zein Drugs 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000007730 finishing process Methods 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 235000021190 leftovers Nutrition 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000004252 protein component Nutrition 0.000 description 1
- 102000034272 protein filaments Human genes 0.000 description 1
- 108091005974 protein filaments Proteins 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
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
- D01F2/06—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
- D01F2/08—Composition of the spinning solution or the bath
-
- 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
- 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
Landscapes
- 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)
- Multicomponent Fibers (AREA)
Abstract
The invention provides a preparation method of regenerated protein composite cellulose fibers, which comprises the steps of preparing a mixed solution of modified zeolite and protein micropowder, preparing a blended spinning solution and spinning. The invention solves the problem that the protein micro powder is difficult to filter due to swelling; meanwhile, the loss of protein can be safely and effectively reduced while aldehyde substances or heavy metal chromium salt is not used; the preparation method of the fiber greatly reduces the loss of protein in the processes of filtering, spinning and refining, and the loss rate is 19-30%; the method not only reduces the loss of protein compared with the blending spinning of alkali dispersion protein powder and viscose, but also does not generate environmental pollution, and is safer for human bodies than the prior art that aldehyde substances are added for acetalization or heavy metal salts are used for solidification.
Description
Technical Field
The invention relates to a protein composite cellulose fiber and a preparation method thereof, in particular to a method for preparing the protein composite cellulose fiber by taking zeolite and protein micro powder as functional components and cellulose fiber as a matrix, belonging to the technical field of textiles.
Background
With the rapid development of science and technology and the continuous improvement of living standard of people, people have not only required the body to shield against cold, but also pursue the function of safety, comfort, beauty and more practicality. The natural protein fiber has the advantages of good elasticity, strong hygroscopicity, good heat retention and the like, is popular with many consumers, but has high price and hopeful and stopped. The extracted animal and plant proteins are added into the spinning solution and blended into filaments, which is a great breakthrough of the protein fiber preparation technology, the finished product not only keeps the characteristics of natural protein fibers, but also has moderate price, and the high-efficiency and high-added-value utilization of the proteins is realized.
Scholars abroad at the end of the 19 th century have already studied regenerated protein fibers, and China has also preliminarily studied the regenerated protein fibers in the last 50 th century. The regenerated protein fiber can be divided into regenerated animal protein fiber and regenerated plant protein fiber according to raw material sources, the natural resources of animals and plants in China are rich, but some resources are directly discarded without being fully utilized, and particularly, the regenerated animal protein fiber is low-grade natural protein fiber such as leftovers of wool and silk, feathers, other animal hair and the like. The excellent processability and serviceability of the cellulose fiber are accepted by the market, the industrial production of the regenerated protein cellulose fiber is realized at present, but the protein loss problem generally exists in the production, the loss is more serious when the addition amount is more, the fiber with high protein content cannot be produced, and the resource waste and the environmental pollution are caused by the loss. At present, the ways for preventing the loss are crosslinking, solidification and the like, and substances such as metal ions, aldehydes and the like are introduced, so that the quality of protein fibers is influenced, and the safety of taking the protein fibers is worried.
The main reason for the loss of protein is that the inherent structure of protein determines its acid and alkali resistance. The protein has stronger resistance to acid action than cotton, and the weak solution of weak acid or strong acid has no obvious destructive effect on the protein at low temperature or normal temperature, and the destructive effect of the acid on the protein is correspondingly intensified along with the increase of the temperature and the concentration. The resistance of protein to alkali is much lower than that of cellulose, and the regenerated cellulose fiber is inevitably contacted with alkali in the production process, so that the protein loss is caused.
At present, many patents related to protein fibers exist, and a Chinese patent with application number of 200710097723.8 discloses a method for manufacturing protein viscose fibers by using animal protein and plant fibers.
Chinese patent application nos. 200410010327.3 and 200510111710.2 disclose a method for producing a blended fiber of soybean protein and viscose, in which a soybean protein liquid and viscose are blended and spun, and then acetalization is performed using aldehydes such as formaldehyde, and finally a finished product is obtained.
The Chinese patent with application number of 201010202726.5 discloses a silkworm pupa protein fiber and a production process thereof, wherein silkworm pupas are dissolved into silkworm pupa protein filaments, and then a cross-linking agent is added for suction filtration, washing and drying. This method requires extraction of proteins and cross-linking with aldehydes.
The chinese patent with application number 201210180771.4 discloses a method for preparing cellulose protein fiber, which is simple in production process, but has the problem of protein loss.
By combining the production technologies of protein fibers disclosed at home and abroad at present, no matter viscose fibers (such as silkworm pupa protein viscose fibers and jade silkworm fibers) or other synthetic fibers (such as soybean protein fibers) spun by a wet method, the method for preventing the protein loss is to add a curing agent for curing, so that aldehyde substances are inevitably used for acetalization when protein liquid is cured or heavy metal chromium salts are used for denaturation and curing, the quality of the protein fibers is influenced, and the substances can cause the deterioration of production conditions and environmental pollution. How to safely and efficiently prevent protein loss is an important direction for the continuous development of protein fibers.
In the swelling process of the protein micropowder, the particle size is increased, so that the filtering is difficult, and the protein with large particle size is filtered by the filter cloth, so that the protein content is reduced and the raw material is wasted.
Disclosure of Invention
The invention aims to solve the problems of the preparation technology of the protein fiber and the current research situation, and provides the protein composite cellulose fiber and the preparation method thereof, wherein the production process is simple, zeolite, protein micropowder, cellulose pulp and the like are used as main raw materials, the zeolite is modified, the protein micropowder is modified and the zeolite is compounded, the modified protein micropowder is adsorbed in the zeolite by utilizing a cage-shaped structure of the zeolite and uniformly dispersed in a cellulose solution, and then the protein composite cellulose fiber is prepared by a wet spinning process, so that the following technical problems are solved:
(1) the problem that the protein micro powder is difficult to filter due to swelling is solved;
(2) the loss of protein is safely and effectively reduced while aldehyde substances or heavy metal chromium salt is not used.
In order to solve the technical problems, the technical solution of the invention is as follows:
a preparation method of protein composite cellulose fiber,
the method comprises the following steps:
1. preparation of activated modified zeolite and modified protein micropowder
(1) Activation modification of zeolite: mixing zeolite and 0.5-1.0 mol/L acid according to a mass ratio of 1: 5-10, adding the mixture into a reaction kettle, stirring for 1-3 hours at a temperature of 60-80 ℃ and a rotating speed of 400-800 r/min, filtering, washing, separating after activation, drying for 2-3 hours at a temperature of 200-400 ℃, grinding the dried zeolite by using a ball mill, and screening out 1-2 micron zeolite powder.
Preferably, the acid is an inorganic acid or an organic acid;
more preferably, the acid is one of acetic acid, nitric acid, sulfuric acid and hydrochloric acid.
(2) Preparing modified protein micropowder liquid: mixing protein micro powder with the particle size of less than 0.9 micron and deionized water according to the mass ratio of 1: 5-10, adding 0.05-1 wt% of dispersing agent for the protein micro powder, adjusting the pH value of the mixed solution to 3.5-5.2 by using acid, adjusting the temperature to 18-22 ℃, and stirring for 1-2 hours to obtain the modified protein micro powder solution.
Preferably, the dispersant is a polyoxyethylene alkylamine, which is soluble in an acidic aqueous solution.
The acid is inorganic acid;
further, the acid is hydrochloric acid, sulfuric acid, nitric acid, or the like.
The protein micro powder can be various animal protein micro powder and plant protein micro powder.
(3) Preparing a mixed solution of zeolite and protein micropowder: adding activated and modified zeolite into the modified protein micropowder liquid according to the mass ratio of 1.2-1.5: 1 of the effective protein micropowder, and stirring for 1-2 hours at 18-22 ℃ to ensure that the protein micropowder fully enters into a zeolite cavity or is adsorbed by zeolite to obtain a mixed liquid of the zeolite and the protein micropowder.
2. Preparing a blended spinning solution: cellulose pulp is used as a raw material, viscose is prepared through the steps of dipping, squeezing, crushing, ageing, yellowing, dissolving, mixing, filtering, defoaming and the like, a protein micro powder solution adsorbed by the prepared zeolite, which accounts for 2.5-4.0 wt% of the content of alpha cellulose calculated according to the effective components of protein, is added into spinning glue by using a pre-spinning injection system, and the mixture is uniformly mixed by a dynamic mixer to obtain a blending spinning solution.
The spinning glue comprises 8.80-9.20% of methyl fiber, 4.40-5.00% of alkali, 30-45 s of viscosity and 8.0-14.0 ml of ripening degree (10% of ammonium chloride value).
3. Spinning and post-treatment: and (3) the blended spinning solution enters a coagulating bath for spinning, and the tows are subjected to multistage drafting to obtain formed tows. The obtained tows are subjected to post-treatment processes such as cutting, desulfurization, washing, oiling, drying and the like to obtain the protein composite cellulose fiber.
Preferably, the coagulating bath contains 80-130 g/L of sulfuric acid and 300-360 g/L of sodium sulfate.
Preferably, the concentration of the sodium sulfite for the desulfurization bath is 2.0-6.0 g/L.
The modified protein micropowder liquid prepared by the invention controls the specific pH and adopts the specific dispersant to disperse the protein micropowder, so that the protein micropowder is dispersed more uniformly, and the prepared modified protein micropowder liquid can make the protein micropowder enter cavities of the zeolite more easily or adsorb more protein micropowder by the zeolite.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following beneficial effects:
(1) the zeolite adsorbs protein micropowder under acidic condition, the combination of the two is added into alkaline viscose, acid is neutralized, the protein micropowder elastically swells in the cavity of the zeolite under alkaline condition in multiple volume, and is more tightly combined with the zeolite, so that the problem of difficult filtration caused by protein swelling is solved; meanwhile, the loss of protein can be safely and effectively reduced without using aldehyde substances or heavy metal chromium salt.
The preparation method of the fiber greatly reduces the loss of protein in the processes of filtering, spinning and refining, and the loss rate is 19-30%; the method can reduce the loss of protein compared with the method of blending and spinning the alkali-dispersed protein powder and viscose liquid, does not cause environmental pollution, and is safer for human bodies than the prior art of adding aldehyde substances for acetalization or using heavy metal salts for solidification.
(2) The protein composite cellulose fiber prepared by the invention contains 2.0-2.8 wt% of protein, and the dry breaking strength of the fiber is more than or equal to 2.10cN/dtex, and the wet breaking strength is more than or equal to 1.10 cN/dtex.
(3) The protein composite cellulose fiber prepared by the method has high dye-uptake and good color fastness, and the protein loss is little in the dyeing and finishing process.
(4) The protein micro powder can be animal protein or plant protein, and can be powder made of various proteins such as wool protein, feather protein, silkworm pupa protein, soybean protein, corn protein and the like, so that the applicability is strong, and the production process is simple.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and description, and is in no way intended to limit the invention.
Example 1:
1. preparation of activated modified zeolite and modified protein micropowder
(1) Activation modification of zeolite: mixing zeolite and 0.5 mol/L hydrochloric acid according to the mass ratio of 1:10, adding into a reaction kettle, stirring for 1 hour at the temperature of 80 ℃ and the rotating speed of a stirrer of 400r/min, filtering, washing with water, separating after activation, drying for 3 hours at the temperature of 200 ℃, grinding the dried zeolite by using a ball mill, and screening out 1-2 micron zeolite powder.
(2) Preparing modified protein micropowder liquid: mixing wool protein micro powder with the particle size of 0.9 micron and deionized water according to the mass ratio of 1:5, adding polyoxyethylene alkylamine accounting for 0.05wt% of the wool protein micro powder, adjusting the pH value of the mixed solution to 4.5 by hydrochloric acid, stirring at the temperature of 18 ℃ for 2 hours, and obtaining the modified wool protein micro powder solution.
(3) Preparing a mixed solution of zeolite and protein micropowder: adding activated and modified zeolite into the modified protein micropowder liquid according to the mass ratio of 1.2:1 of the effective protein micropowder, and stirring for 2 hours at 18 ℃ to ensure that the protein micropowder fully enters into cavities of the zeolite or is adsorbed by the zeolite to obtain a mixed liquid of the zeolite and the protein micropowder.
2. Preparing a blended spinning solution: cellulose pulp is used as a raw material, viscose is prepared by the steps of dipping, squeezing, crushing, ageing, yellowing, dissolving, mixing, filtering, defoaming and the like, protein liquid adsorbed by the prepared zeolite and accounting for 4.0wt% of the content of alpha cellulose in terms of protein active ingredients is added into spinning glue by a pre-spinning injection system, and the mixture is uniformly mixed by a dynamic mixer to obtain the blended spinning solution.
3. Spinning and post-treatment: and (3) spinning the blended spinning solution in a coagulating bath of 80g/L sulfuric acid and 300g/L sodium sulfate, and performing multistage drafting on tows to obtain formed tows. The obtained tows are subjected to post-treatment processes of cutting, desulfurization by using 2.0g/L sodium sulfite, washing, oiling, drying and the like to obtain the protein composite cellulose fiber.
The indexes of the fiber prepared by the process of the embodiment are as follows:
dry breaking strength: 2.10 cN/dtex;
wet breaking strength: 1.11 cN/dtex;
dry elongation at break: 16.4 percent;
protein content: 2.80 percent.
Under the condition that other processes are not changed, the protein micropowder which has the same content as that of the protein micropowder obtained in the previous embodiment and is not adsorbed by zeolite is added into spinning glue for spinning, and the protein content of the detected fiber is 1.25%.
Example 2:
1. preparation of activated modified zeolite and modified protein micropowder
(1) Activation modification of zeolite: mixing zeolite and 1 mol/L nitric acid according to a mass ratio of 1:5, adding the mixture into a reaction kettle, stirring for 3 hours at a temperature of 60 ℃ and a rotating speed of 800r/min, filtering, washing, separating after activation, drying for 2 hours at 400 ℃, grinding the dried zeolite by using a ball mill, and screening out 1-2 micron zeolite powder.
(2) Preparing modified protein micropowder liquid: mixing soybean protein micropowder with the particle size of 0.9 micron and deionized water according to the mass ratio of 1:8, adding polyoxyethylene alkylamine accounting for 1wt% of the soybean protein micropowder, adjusting the pH value of the mixed solution to 4.2 by using sulfuric acid, stirring at the temperature of 22 ℃ for 1 hour, and obtaining modified soybean protein micropowder liquid.
(3) Preparing a mixed solution of zeolite and protein micropowder: adding activated and modified zeolite into the modified protein micropowder liquid according to the mass ratio of 1.5:1 of the effective protein micropowder, and stirring for 1 hour at 22 ℃ to ensure that the protein micropowder fully enters into cavities of the zeolite or is adsorbed by the zeolite to obtain a mixed liquid of the zeolite and the protein micropowder.
2. Preparing a blended spinning solution: cellulose pulp is used as a raw material, viscose is prepared by the steps of dipping, squeezing, crushing, ageing, yellowing, dissolving, mixing, filtering, defoaming and the like, protein micro powder liquid absorbed by the prepared zeolite, which accounts for 3.5wt% of the content of alpha cellulose calculated according to the effective components of protein, is added into spinning glue by a pre-spinning injection system, and the mixture is uniformly mixed by a dynamic mixer to obtain blended spinning liquid.
3. Spinning and post-treatment: and (3) spinning the blended spinning solution in a coagulating bath containing 100g/L sulfuric acid and 320g/L sodium sulfate, and drawing the tows in multiple stages to obtain the formed tows. The obtained tows are subjected to post-treatment processes of cutting, desulfurization by using 4.0g/L sodium sulfite, washing, oiling, drying and the like to obtain the protein composite cellulose fiber.
The indexes of the fiber prepared by the process of the embodiment are as follows:
dry breaking strength: 2.15 cN/dtex;
wet breaking strength: 1.13 cN/dtex;
dry elongation at break: 17.2 percent;
protein content: 2.65 percent.
Example 3:
1. preparation of activated modified zeolite and modified protein micropowder
(1) Activation modification of zeolite: mixing zeolite and 0.8 mol/L sulfuric acid according to a mass ratio of 1:8, adding into a reaction kettle, stirring for 2 hours at a temperature of 70 ℃ and a rotating speed of 500r/min, filtering, washing and separating after activation, drying for 2.5 hours at 350 ℃, grinding the dried zeolite by using a ball mill, and screening out 1-2 micron zeolite powder.
(2) Preparing modified protein micropowder liquid: mixing the silkworm pupa protein micro powder with the particle size of 0.9 micron and deionized water according to the mass ratio of 1:6, adding polyoxyethylene alkylamine accounting for 0.08wt% of the protein micro powder, adjusting the pH value of the mixed solution to 4.4 by using sulfuric acid, adjusting the temperature to 19 ℃, and stirring for 1.5 hours to obtain the modified protein micro powder solution.
(3) Preparing a mixed solution of zeolite and protein micropowder: adding activated and modified zeolite into the modified protein micropowder liquid according to the mass ratio of 1.3:1 of the effective protein micropowder, and stirring for 1.5 hours at 20 ℃ to ensure that the protein micropowder fully enters cavities of the zeolite or is adsorbed by the zeolite to obtain a mixed liquid of the zeolite and the protein micropowder.
2. Preparing a blended spinning solution: cellulose pulp is used as a raw material, viscose is prepared by the steps of dipping, squeezing, crushing, ageing, yellowing, dissolving, mixing, filtering, defoaming and the like, protein liquid adsorbed by the prepared zeolite, which accounts for 3.0wt% of the content of alpha cellulose in terms of protein active ingredients, is added into spinning glue by a pre-spinning injection system, and the mixture is uniformly mixed by a dynamic mixer to obtain blended spinning liquid.
3. Spinning and post-treatment: and (3) spinning the blended spinning solution in a coagulating bath of 120g/L sulfuric acid and 340g/L sodium sulfate, and performing multistage drafting on tows to obtain formed tows. The obtained tows are subjected to post-treatment processes of cutting, desulfurization by using 5.0g/L sodium sulfite, washing, oiling, drying and the like to obtain the protein composite cellulose fiber.
The indexes of the fiber prepared by the process of the embodiment are as follows:
dry breaking strength: 2.19 cN/dtex;
wet breaking strength: 1.16 cN/dtex;
dry elongation at break: 17.6 percent;
protein content: 2.26 percent.
Example 4:
1. preparation of activated modified zeolite and modified protein micropowder
(1) Activation modification of zeolite: mixing zeolite and 0.9 mol/L hydrochloric acid according to the mass ratio of 1:6, adding into a reaction kettle, stirring for 2.5 hours at the temperature of 75 ℃ and the rotating speed of 550r/min, filtering, washing and separating after activation, drying for 2 hours at the temperature of 320 ℃, grinding the dried zeolite by using a ball mill, and screening out 1-2 micron zeolite powder.
(2) Preparing modified protein micro-liquid: mixing zein micropowder with the particle size of 0.9 micron and deionized water according to the mass ratio of protein to water of 1:7, adding polyoxyethylene alkylamine accounting for 0.08wt% of the zein micropowder, adjusting the pH value of the mixed solution to 4.7 by hydrochloric acid at the temperature of 20 ℃, and stirring for 1 hour to obtain the modified protein micropowder liquid.
(3) Preparing a mixed solution of zeolite and protein micropowder: adding activated and modified zeolite into the modified protein micropowder liquid according to the mass ratio of 1.4:1 of the effective protein micropowder, and stirring for 1 hour at 20 ℃ to ensure that the protein micropowder fully enters into cavities of the zeolite or is adsorbed by the zeolite to obtain a mixed liquid of the zeolite and the protein micropowder.
2. Preparing a blended spinning solution: cellulose pulp is used as a raw material, viscose is prepared by the steps of dipping, squeezing, crushing, ageing, yellowing, dissolving, mixing, filtering, defoaming and the like, protein liquid adsorbed by the prepared zeolite accounting for 2.5wt% of the effective protein component is added into spinning glue by a pre-spinning injection system, and the mixture is uniformly mixed by a dynamic mixer to obtain blended spinning liquid.
3. Spinning and post-treatment: and (3) spinning the blended spinning solution in a coagulating bath containing 130g/L sulfuric acid and 360g/L sodium sulfate, and drawing the tows in multiple stages to obtain formed tows. The obtained tows are subjected to post-treatment processes of cutting, desulfurization by using 2.0g/L sodium sulfite, washing, oiling, drying and the like to obtain the protein composite cellulose fiber.
The fiber prepared by the process of the embodiment has the following indexes:
dry breaking strength: 2.21 cN/dtex;
wet breaking strength: 1.15 cN/dtex;
dry elongation at break: 18.1 percent;
protein content: 2.02 percent.
Unless otherwise specified, the proportions used in the present invention are mass ratios, and the percentages used are mass percentages.
Claims (1)
1. A preparation method of regenerated protein composite cellulose fiber is characterized by comprising the following steps: the preparation method comprises the steps of preparing a mixed solution of zeolite and protein micropowder, preparing a blended spinning solution and spinning;
preparing a mixed solution of the zeolite and the protein micropowder, namely mixing and stirring activated and modified zeolite and a modified protein micropowder solution to obtain a mixed solution of the zeolite and the protein micropowder; the mass ratio of the activated and modified zeolite to the protein micro powder is 1.2-1.5: 1; performing activation modification on the zeolite, namely mixing and stirring the zeolite and acid, and then drying and grinding to obtain 1-2 micron zeolite powder; the acid is one of acetic acid, nitric acid, sulfuric acid and hydrochloric acid;
the mass ratio of the zeolite to the acid is 1: 5-10; the concentration of the acid is 0.5-1.0 mol/L; mixing and stirring at the temperature of 60-80 ℃;
stirring for 1-3 hours at the rotating speed of 400-800 r/min;
the preparation method of the modified protein micropowder liquid comprises the steps of mixing protein micropowder and deionized water, adding a dispersing agent, adjusting the pH value to 3.5-5.2, and stirring to uniformly disperse the protein micropowder to obtain the modified protein micropowder liquid;
the particle size of the protein micro powder is below 0.9 micron, and the mass ratio of the protein micro powder to the deionized water is 1: 5-10; the mass percentage of the dispersing agent relative to the protein micro powder is 0.05-1%;
the dispersing agent is polyoxyethylene alkylamine;
preparing the blended spinning solution, namely adding a zeolite and protein micro powder mixed solution which accounts for 2.5-4.0 wt% of the content of the alpha cellulose calculated according to protein effective components into spinning glue, and uniformly mixing to obtain the blended spinning solution; the coagulating bath adopted in the spinning comprises 80-130 g/L of sulfuric acid and 300-360 g/L of sodium sulfate.
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