CN112824587A - Tea saponin modified cellulose fabric for removing chromium ions in water and preparation method thereof - Google Patents

Tea saponin modified cellulose fabric for removing chromium ions in water and preparation method thereof Download PDF

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CN112824587A
CN112824587A CN201911151797.4A CN201911151797A CN112824587A CN 112824587 A CN112824587 A CN 112824587A CN 201911151797 A CN201911151797 A CN 201911151797A CN 112824587 A CN112824587 A CN 112824587A
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tea saponin
modified
cellulose
fiber
fabric
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董永春
顾家玉
张佳璇
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Tianjin Polytechnic University
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Tianjin Polytechnic University
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/224—Esters of carboxylic acids; Esters of carbonic acid
    • D06M13/2246—Esters of unsaturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/70—Treatment of water, waste water, or sewage by reduction
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/22—Chromium or chromium compounds, e.g. chromates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic

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  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

The invention discloses a tea saponin modified cellulose fabric for removing chromium ions in water and a preparation method thereof. The method modifies the saponin compounds for the first time, and when the method is used for a finishing process of cellulose fibers, a large amount of carboxyl can be effectively introduced into a cellulose fiber molecular chain, the carboxyl content of a finished product is rich, the quantity of the introduced carboxyl is controllable, the carboxyl and the cellulose fiber molecular chain are firmly combined, the process is simple, the production cost is low, and the method is favorable for industrial popularization. The technical method provided by the invention not only can widen the application of the tea saponin and achieve the purpose of processing waste with waste, but also can ensure that the tea saponin and the cellulose fiber are both easily biodegradable and can not generate the problem of secondary pollution. And the reduction performance of the tea saponin loaded on the surface of the fiber can reduce Cr (VI) into Cr (III), and the modified fabric can fix the generated Cr (III) on the surface of the fiber by virtue of adsorption, so as to carry out deep purification treatment on the water body.

Description

Tea saponin modified cellulose fabric for removing chromium ions in water and preparation method thereof
Technical Field
The invention relates to the field of environment purification materials, in particular to a preparation method of a tea saponin modified cellulose fabric for removing chromium ions in water.
Background
Cellulose fibers, which are the most widely used natural fibers in modern industries, are linear macromolecules composed of glucose ring compounds in which cellulose is linked to each other by 1, 4-glycosidic bonds, and a large number of hydroxyl groups are present in the molecular structure. After a large amount of carboxyl is introduced to a cellulose fiber molecular chain, the effects of improving skin-friendly property, ultraviolet resistance, moisture absorption, air permeability and the like of the cellulose fiber molecular chain are improved, and the cellulose fiber molecular chain is an indispensable raw material and auxiliary material in the fields of food packaging, medical treatment and health, daily chemical industry and the like. Generally, there are two methods for introducing carboxyl groups into the molecular chain of Cellulose fiber, the most common method is modification reaction of Cellulose fiber by using polycarboxylic acid, which can graft a large amount of carboxyl groups to Cellulose fabric quickly and effectively, but the consumption of polycarboxylic acid in the actual production process is huge, so that the production cost is significantly increased [1.Li B, Dong Y, Li l. 1295-1309.]. Secondly, chloroacetic acid is used for directly grafting carboxyl on a cellulose fiber molecular chain through etherification reaction under an alkaline condition, the method is simple and easy to implement, but the process adopts over high caustic soda concentration, so that not only can the mechanical strength of the cellulose fabric be reduced, but also high-alkali-content wastewater can be discharged, so that the serious ecological environment pollution problem is caused, and the harm to human health is caused [2. Yan Yonghai, Zhuping, Sushuying, et al. carboxymethylation modification of the cellulose fabric [ J ] printing and dyeing, 2013 (06): 36-38+42.]. Therefore, we have to find a process for carboxylation modified cellulose fiber which is efficient, environment-friendly, simple in process and low in cost.
The tea saponin is an important natural functional compound extracted from tea seed oil waste residue, and the main component of the tea saponin is pentacyclic triterpenoid saponin with the relative molecular weight of about 1200. The molecular structure of the tea saponin contains hydrophilic groups and hydrophobic groups, is a natural nonionic surfactant, has good functions of emulsification, dispersion, foaming, wetting and the like, and is widely applied to the fields of textile, medicine, daily chemical industry and the like. In addition, the tea saponin has good reduction performance and metal chelating capacity, and has an inhibiting effect on oxidation substances such as hydroxyl free radicals and the like. However, due to the structural complexity, no report about the tea saponin modification technology is found at home and abroad at present.
Chromium compounds have been widely used as important industrial raw materials for the last two decades, resulting in the production of large amounts of chromium-containing industrial waste water. This not only causes serious problems of ecological environmental pollution, but also harms human health. Research proves that Cr (VI) in water body is usually CrO4 2-、HCrO4 -And Cr2O7 2-The water body is yellow due to the existence of the forms, and the water body has strong biological toxicity, can cause chronic poisoning of a human body to further induce various cancers, and is listed as a priority pollutant by a multi-national environmental protection agency. While cr (iii) in water exists mainly in the form of hydrated ionic complexes, which are about one percent toxic to cr (vi). At present, the chromium-containing wastewater treatment technologies mainly comprise an oxidation-reduction method, a chemical precipitation method, a biological technology, an adsorption method and the like, and although the technologies have certain effects on the purification of the chromium-containing wastewater, the technologies have the problems of high treatment cost, secondary pollution caused by the generation of a large amount of chromium sludge and the like to different degrees.
The invention provides a method for removing chromium ions in a water body by using tea saponin modified fabric, which is used for modifying saponin compounds for the first time, can effectively introduce a large amount of carboxyl on cellulose fiber molecular chains, has rich carboxyl content of finished products, controllable carboxyl quantity, firm combination of the carboxyl and the cellulose fiber molecular chains, simple process and low production cost, and is beneficial to industrial popularization. The technical method not only can broaden the application of the tea saponin and achieve the purpose of processing waste with waste, but also can lead the tea saponin and the cellulose fiber to be easily biodegradable and not to generate the problem of secondary pollution. And the reduction performance of the tea saponin loaded on the surface of the fiber can reduce Cr (VI) into Cr (III), and the modified fabric can fix the generated Cr (III) on the surface of the fiber by virtue of adsorption, so as to carry out deep purification treatment on the water body.
Disclosure of Invention
Aiming at the defects of the prior art, the technical problems to be solved by the invention are as follows: a tea saponin modified cellulose fabric for removing chromium ions in water and a preparation method thereof are disclosed, the method modifies saponin compounds for the first time, and the modification method is used for a finishing process of cellulose fibers, can effectively introduce a large amount of carboxyl on cellulose fiber molecular chains, has rich carboxyl content of finished products, controllable carboxyl quantity, firm combination of the carboxyl and the cellulose fiber molecular chains, simple process and low production cost, and is beneficial to industrial popularization. The technical method provided by the invention not only can widen the application of the tea saponin and achieve the purpose of processing waste with waste, but also can ensure that the tea saponin and the cellulose fiber are both easily biodegradable and can not generate the problem of secondary pollution. And the reduction performance of the tea saponin loaded on the surface of the fiber can reduce Cr (VI) into Cr (III), and the modified fabric can fix the generated Cr (III) on the surface of the fiber by virtue of adsorption, so as to carry out deep purification treatment on the water body. Meanwhile, the saponin material can be saponin compounds such as tea saponin, ginsenoside or ganoderma saponin and the like, and the cellulose fiber can be cellulose fiber such as cotton fiber, hemp fiber or viscose fiber and the like. The specific method comprises the following steps:
1. pretreatment of tea saponin: fully dissolving 10g of tea saponin into 300ml of water, and filling the solution into a dialysis bag for treatment for 12 hours to separate out and remove small molecular impurities. Then the trapped fluid is frozen and dried, and then is repeatedly cleaned by ethanol and dried to obtain a light yellow powdered tea saponin refined product;
2. pretreatment of cellulose fibers: firstly, treating cellulose fiber by using a tea saponin aqueous solution with the concentration of 2g/L at 50 ℃ under the stirring condition for 30 minutes, and then taking out, washing and drying;
3. modification reaction of tea saponin: firstly, accurately weighing 1g of refined tea saponin powder in the first step, dissolving the refined tea saponin powder in 100ml of 60% ethanol solution, swelling for 30 minutes, then adding 0.05g-0.4g of sodium hydroxide into the solution, fully dissolving, wherein the concentration of the sodium hydroxide in the solution is 0.5g/L-4g/L, fully stirring for 20 minutes, adding 0.2g of monochloroacetic acid into the solution, keeping the temperature in a water bath at 60 ℃ for 3 hours, then adjusting the pH value of the solution to 5-6 by using glacial acetic acid, finally drying at 60 ℃ to obtain a tan powdered modified tea saponin product, and calculating the substitution degree (DS value) of the modified tea saponin powder by using an acid-base titration method;
4. the process for treating the cellulose fabric by using the modified tea saponin comprises the following steps: taking 1g-5g of modified tea saponin powder to fully dissolve in 100ml of water solution, then putting 5g of cellulose fabric into carboxymethylated tea saponin solution to perform dipping treatment for 20 minutes, removing redundant water of the fabric, drying the fabric at 100 ℃, reacting at 180 ℃ for 1.5 minutes to obtain a tan modified tea saponin finished cellulose fabric sample, and calculating the carboxylic acid content value of the cellulose fiber surface by using an acid-base titration method.
Compared with the prior art, the method firstly performs carboxymethylation modification on tea saponin, introduces carboxyl in the molecular structure of the tea saponin, and then loads the tea saponin on the surface of the cellulose fabric through esterification reaction. For example, reference 1[1.Li B, Dong Y, Li L.preparation and catalytic performance of Fe (III) -citric acid-modified cotton fiber complex as a novel Cellulose fiber-supported heterologous photo-to-Fenton catalyst [ J ]. Cellulose, 2015, 22 (2): 1295. 1309.] wherein the cellulose fibers are provided with carboxyl groups using citric acid at a concentration of 200g/L, the cellulose fibers have a DS value (DS value is the average number of hydroxyl groups substituted per anhydroglucose unit in the cellulose molecule) of 0.191; comparison document 2[2. Yan Yonghai, Zhuping, Sushuying, et al carboxymethylation modification of cotton fabrics [ J ] printing and dyeing, 2013 (06): 36-38+42 ] performing carboxymethylation modification on the cotton fabric by using sodium hydroxide with the concentration of 250g/L, wherein the DS value of the cotton fiber is 0.36; in the process, the concentration of sodium hydroxide is 2g/L, the dosage of the modified tea saponin is 20g/L, and the DS value of the cotton fiber is 0.38, so that the novel method for introducing carboxyl into the cellulose fabric by using the modified tea saponin has advancement. And the tea saponin modified cellulose fabric can reduce Cr (VI) into Cr (III) and fix the generated Cr (III) on the surface of the fabric, so as to carry out deep purification treatment on the water body. Therefore, the tea saponin modified cellulose fabric for removing the chromium ions in the water and the preparation method thereof have the advantages of being advanced.
Drawings
FIG. 1 is a graph showing the effect of different amounts of NaOH on DS of tea saponin as described in examples 1-5 of the present invention.
FIG. 2 shows the influence of the addition of different modified tea saponin on the loading of tea saponin on the surface of cotton fabric.
Fig. 3 shows the hexavalent chromium ion removal rate (R%) and the total chromium ion removal rate (μ%) of cotton fabrics with different tea saponin loadings and iron ion modification in example 6 of the present invention.
Detailed Description
Provides a tea saponin modified cellulose fabric for removing chromium ions in water and a preparation method thereof. The method is characterized by mainly comprising four steps of firstly modifying the tea saponin by using low-concentration sodium hydroxide, then introducing a large amount of carboxyl on a cotton fiber molecular chain by using the modified tea saponin and removing chromium ions in the wastewater. The concentration of the sodium hydroxide aqueous solution is 0.5g/L-2g/L, and the fiber material can be cellulose fiber such as cotton fiber, hemp fiber or viscose fiber. The method is used for treating cellulose fibers by using the modified tea saponin, introduces carboxyl into a cellulose fiber molecular chain, and has the advantages of low alkali concentration and modified tea saponin consumption, and considerable introduced carboxyl quantity. Meanwhile, the saponin material can be saponin compounds such as tea saponin, ginsenoside or ganoderma saponin and the like.
Specific embodiments of the present invention are described below, but the claims of the present invention are not limited to these specific embodiments.
Example 1
1. Pretreatment of tea saponin: fully dissolving 10g of tea saponin into 300ml of water, and filling the solution into a dialysis bag for treatment for 12 hours to separate out and remove small molecular impurities. Then the trapped fluid is frozen and dried, and then is repeatedly cleaned by ethanol and dried to obtain a light yellow powdered tea saponin refined product;
2. pretreatment of cotton fibers: firstly, treating cotton fiber for 30 minutes by using a tea saponin aqueous solution with the concentration of 2g/L at the temperature of 50 ℃ under the stirring condition, taking out, washing and drying;
3. modification reaction of tea saponin: firstly, accurately weighing 1g of refined tea saponin powder in the step 1, dissolving the refined tea saponin powder in 100ml of 60% ethanol solution, swelling for 30 minutes, then adding 0.05g of sodium hydroxide into the solution to be fully dissolved, wherein the concentration of the sodium hydroxide in the solution is 0.5g/L, adding 0.2g of monochloroacetic acid into the solution after 20 minutes, preserving the heat in a water bath at 60 ℃ for 3 hours, neutralizing the pH value of the solution by glacial acetic acid for 5-6, finally drying at 60 ℃ to obtain a tan powdery modified tea saponin product, and calculating the substitution degree (DS value) of the modified tea saponin powder by using an acid-base titration method;
4. the process for treating cotton fabrics by using the modified tea saponin comprises the following steps: fully dissolving 5g of modified tea saponin powder in 100ml of aqueous solution, then putting 5g of cotton fabric into carboxymethylated tea saponin solution for dipping treatment for 20 minutes, removing excessive moisture of the fabric, drying the fabric at 100 ℃, reacting at 180 ℃ for 1.5 minutes to obtain a tan modified tea saponin finished cotton fabric sample, and calculating the carboxylic acid content on the surface of the cotton fiber by using an acid-base titration method.
Example 2
1. The process was the same as in step 1 of example 1.
2. The procedure was the same as in step 2 of example 1.
3. The concentration of sodium hydroxide was set to 1g/L, and the rest of the process was the same as in step 3 of example 1.
4. The process was the same as in step 4 of example 1.
Example 3
1. The process was the same as in step 1 of example 1.
2. The procedure was the same as in step 2 of example 1.
3. The concentration of sodium hydroxide was set to 2g/L, and the rest of the process was the same as in step 3 of example 1.
4. The process was the same as in step 4 of example 1.
Example 4
1. The process was the same as in step 1 of example 1.
2. The procedure was the same as in step 2 of example 1.
3. The concentration of sodium hydroxide was set to 3g/L, and the rest of the process was the same as in step 3 of example 1.
4. The process was the same as in step 4 of example 1.
Example 5
1. The process was the same as in step 1 of example 1.
2. The procedure was the same as in step 2 of example 1.
3. The concentration of sodium hydroxide was set to 4g/L, and the rest of the process was the same as in step 3 of example 1.
4. The process was the same as in step 4 of example 1.
Example 6
1. The process was the same as in step 1 of example 1.
2. The procedure was the same as in step 2 of example 1.
3. The process was the same as in step 3 of example 3.
4. The process was the same as in step 4 of example 1.
5. Keeping the bath ratio of the carboxymethylated tea saponin finished cotton fabric at 1: 50, keeping the temperature of the carboxymethylated tea saponin finished cotton fabric in a ferric ion solution with the concentration of 0.1 mol per liter for 2 hours, then thoroughly washing the fabric with tap water, and airing the fabric under natural conditions to obtain iron ion modified carboxymethylated tea saponin finished cotton fabric;
6. putting the iron ion modified carboxymethylated tea saponin finished cotton fabric into a hexavalent chromium ion solution with a constant bath ratio of 1: 100, a concentration of 20 micromole/liter and a pH value of 3-4 to react for 80 minutes, and then removing hexavalent chromium ions.
The invention is further illustrated by the following examples in conjunction with the accompanying drawings. As can be seen from FIG. 1, the DS value of the modified tea saponin is increased along with the increase of the concentration of sodium hydroxide, reaches the maximum value after the DS value is increased to 2g/L, and then is in a descending trend along with the increase of the weight gain rate, which indicates that the optimal value of the concentration of the sodium hydroxide is about 2 percent in the tea saponin modification experiment. As can be seen from fig. 2, the tea saponin loading of the cotton fibers is increased along with the increase of the addition of the modified tea saponin, and the tea saponin loading and DS of the cotton fibers reach the maximum value when the concentration of the modified tea saponin finishing liquid is 20g/L, which indicates that the increase of the addition of the modified tea saponin is beneficial to loading more modified tea saponin on the surface of the cotton fabric, thereby introducing more carboxyl groups to the cotton fabric. Fig. 3 shows that along with the increase of the loading amount of tea saponin on the surface of the cotton fabric, the higher the concentration of the carboxymethylated tea saponin is, the more the increase of the amount of the tea saponin on the cotton fabric is facilitated, the reducibility of the carboxymethylated tea saponin for finishing the cotton fabric is gradually increased, the reduction of hexavalent chromium ions and the adsorption of total chromium ions are facilitated, and particularly, the chromium ion removal efficiency is remarkably improved after iron ion modification.
In conclusion, the process disclosed by the invention not only reduces the use concentration of caustic soda and relieves the discharge pressure of wastewater, but also has low cost of the tea saponin, can achieve the effect similar to that of a large amount of polycarboxylic acid modified cotton fabrics by using a small amount of tea saponin in the carboxylic acid modification process of the cotton fabrics, effectively reduces the production cost, and has advancement. The technical method provided by the invention not only can widen the application of the tea saponin and achieve the purpose of processing waste with waste, but also can ensure that the tea saponin and the cotton fiber are both easily biodegradable and can not generate the problem of secondary pollution. And the reduction performance of the tea saponin loaded on the surface of the fiber can reduce Cr (VI) into Cr (III), and the modified fabric can fix the generated Cr (III) on the surface of the fiber by virtue of adsorption, so as to carry out deep purification treatment on the water body.
The above-mentioned embodiments only express the embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several modifications can be made without departing from the inventive concept, and these modifications belong to the protective scope of the invention.

Claims (4)

1. A modification method of low-alkali low-cost and environment-friendly tea saponin grafted carboxyl is characterized in that the concentration of NaOH is low in the modification process, the concentration of NaOH is 0.5-4 g/L, the appearance of the prepared modified tea saponin is brownish yellow, and the substitution degree is 0.1-0.7.
2. The modified tea saponin finished cellulose fiber which is low in cost, environment-friendly and suitable for industrial production according to claim 1, characterized in that the appearance of the modified tea saponin finished cellulose fiber is brownish yellow, and the loading amount of the modified tea saponin on the cellulose fabric is 30 mg/g to 120 mg/g.
3. The modified tea saponin finished cellulose fiber which is low in cost, environment-friendly and suitable for industrial production, is prepared by adopting the following process according to any one of claims 1 to 2:
the method comprises the following steps: pretreatment of tea saponin: fully dissolving 10g of tea saponin into 300ml of water, and filling the solution into a dialysis bag for treatment for 12 hours to separate out and remove small molecular impurities. Then the trapped fluid is frozen and dried, and then is repeatedly cleaned by ethanol and dried to obtain a light yellow powdered tea saponin refined product;
step two: pretreatment of cellulose fibers: firstly, treating cellulose fiber by using a tea saponin aqueous solution with the concentration of 2 grams per liter at 50 ℃ under the stirring condition for 30 minutes, and then taking out, washing and drying;
step three: modification reaction of tea saponin: firstly, accurately weighing 1g of refined tea saponin powder in the first step, dissolving the refined tea saponin powder in 100ml of 60% ethanol solution, swelling for 30 minutes, then adding 0.05-0.4 g of sodium hydroxide into the solution, fully dissolving, wherein the concentration of the sodium hydroxide in the solution is 0.5-4 g/L, adding 0.2g of monochloroacetic acid into the solution after 20 minutes, keeping the temperature in a water bath at 60 ℃ for 3 hours, adjusting the pH value of the solution to 5-6 by using glacial acetic acid, finally drying at 60 ℃ to obtain a tan powdered modified tea saponin product, and calculating the substitution degree of the modified tea saponin powder by using an acid-base titration method;
step four: the process for treating the cellulose fiber by the modified tea saponin comprises the following steps: taking 1 to 5 grams of modified tea saponin powder to fully dissolve in 100 milliliters of water solution, then putting 5 grams of cellulose fabric into carboxymethylated tea saponin solution for dipping treatment for 20 minutes, removing redundant water of the fabric, drying the fabric at 100 ℃, reacting at 180 ℃ for 1.5 minutes to obtain a tan modified tea saponin finished cellulose fabric sample, and calculating the carboxylic acid content on the surface of the cellulose fiber.
4. The tea saponin of claims 1-2, wherein the tea saponin is selected from the group consisting of ginsenoside and ganoderic saponin, and the cellulose fiber is selected from the group consisting of cotton fiber, hemp fiber and viscose fiber.
CN201911151797.4A 2019-11-21 2019-11-21 Tea saponin modified cellulose fabric for removing chromium ions in water and preparation method thereof Pending CN112824587A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005163194A (en) * 2003-11-28 2005-06-23 Asahi Kasei Chemicals Corp Treating agent for paper or fiber
CN105113233A (en) * 2015-08-31 2015-12-02 安徽天威羊绒制品有限公司 Breathable moisture-adsorption cashmere fiber added with modified aloe viscose fiber and preparation method thereof
CN106988124A (en) * 2017-05-22 2017-07-28 苏州凯邦生物技术有限公司 A kind of alkaline-resisting refinery practice of ion liquid modified ramee
CN108486715A (en) * 2018-05-03 2018-09-04 广东护康宝农林生物科技有限公司 A kind of Tea Saponin washes clean bag and its application method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005163194A (en) * 2003-11-28 2005-06-23 Asahi Kasei Chemicals Corp Treating agent for paper or fiber
CN105113233A (en) * 2015-08-31 2015-12-02 安徽天威羊绒制品有限公司 Breathable moisture-adsorption cashmere fiber added with modified aloe viscose fiber and preparation method thereof
CN106988124A (en) * 2017-05-22 2017-07-28 苏州凯邦生物技术有限公司 A kind of alkaline-resisting refinery practice of ion liquid modified ramee
CN108486715A (en) * 2018-05-03 2018-09-04 广东护康宝农林生物科技有限公司 A kind of Tea Saponin washes clean bag and its application method

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