CN104624249A - Method for preparing loofah sponge-based cation exchange fibers - Google Patents
Method for preparing loofah sponge-based cation exchange fibers Download PDFInfo
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- CN104624249A CN104624249A CN201410842847.4A CN201410842847A CN104624249A CN 104624249 A CN104624249 A CN 104624249A CN 201410842847 A CN201410842847 A CN 201410842847A CN 104624249 A CN104624249 A CN 104624249A
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- luffa
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- cation exchange
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- loofah
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/16—Organic material
- B01J39/18—Macromolecular compounds
- B01J39/22—Cellulose or wood; Derivatives thereof
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- 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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
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Abstract
The invention discloses a method for preparing loofah sponge-based cation exchange fibers. The method comprises the following steps: airing or drying ripened loofah sponges, removing the skin and inside seeds, and shearing into massive loofah sponges; washing and drying the massive loofah sponges by using boiling water, immersing the loofah sponges in a photosensitizer solution for soaking in a shading mode, and soaking until the volatile components are completely volatilized, wherein the photosensitizer solution is prepared by dissolving diphenyl ketone in a volatile organic solvent; immersing the massive loofah sponges obtained in the previous step in a grafting solution, carrying out a grafting reaction under ultraviolet irradiation, washing and performing acetone extraction after the reaction is ended, drying, thereby obtaining the loofah sponge-based cation exchange fibers, wherein the grafting solution refers to an aqueous solution of acrylic acid. The conventional ultraviolet initiation technology is utilized, a method for sequentially performing photosensitizer loading and solution grafting is adopted, the acrylic monomer with functional groups is introduced to the natural loofah sponge surface in a bonding mode, the utilization rate of the grafting monomers is improved, and the obtained fibers are uniform in grafting and high in adsorption capacity and can be repeatedly used.
Description
Technical field
The invention belongs to technical field of composite materials, be specifically related to a kind of preparation method of luffa base cation exchange fibre.
Background technology
Ion exchange material has a wide range of applications in the field of industrial waste water treatment such as effluent containing heavy metal ions, dyeing waste water.At present, the chemical products such as the resin/fiber prepared for raw material with non-renewable fossil energy are the most common on market, are also most widely used ion exchange materials; But along with the consumption of fossil energy and the day by day serious of environmental pollution, utilize natural reproducible resource, the friendly product of development environment and technology will become the inexorable trend of scientific research, and therefore development and utilization natural biomass base ion exchange material has very important meaning.In recent years, carrying out modification preparation to agriculture and forestry organic waste materials such as rice husk, palm, peanut shell, bagasse and luffas, to have the research of the adsorbent of ion exchanging function a lot.
Luffa is the three-dimensional fiber element beam tube of multidirectional fibrage composition in sponge gourd fruit, forms primarily of cellulose, hemicellulose and lignin.Luffa not only has that output is high, cheap, the feature such as degradable and environmental friendliness, and its porous surface, and mechanical performance is superior.Therefore, functional graft modification can be carried out to luffa surface, to give its ion-exchange performance.The method of luffa being carried out to graft modification has a lot, mainly contains chemical graft, high-energy radiation grafting, plasma grafting and Graft copolymerization etc.Though chemical graft equipment is simple, once carry out, very easily there is homopolymerization and reaction condition is wayward in reaction.High-energy radiation and plasma grafting reaction relatively rapid, grafting scope can control, but to the condition of grafting and equipment requirement higher, and have injury to material main body.Though above grafting method can realize grafting object, there is the common fault that percent grafting is low, grafting cost is high, utilization rate that is monomer is low, not easily realize large-scale production.Comparatively speaking, Graft copolymerization more easily realizes grafting object, its principle is by UV-irradiation technology, under the effect of sensitising agent, the large molecule containing active group is fixed by the mode of chemical bonding (grafting) can to realize material for a long time modification performance at substrate surface.Patent CN103223354 discloses and a kind of carries out grafting modification through series of steps such as pretreatment, activation, crosslinked, grafting to luffa, have short, power consumption consuming time less, preparation cost is low, and the absorption property of product is good, reclaims and regenerate the features such as simple and convenient.Patent CN103566907, patent CN104447009 and patent CN103933950 disclose respectively and carry out modifying its good absorption property of imparting to luffa with pyromellitic acid anhydride, cysteine and solid-loaded ionic-liquid, product is mechanical performance and repeat performance all preferably, all has good adsorption capacity to containing heavy metal ion such as chromium, copper, lead, mercury.
Summary of the invention
The object of the invention be to provide a kind of simple to operate, grafting is even, adsorption capacity is large, can the preparation method of reusable cation exchange fibre
For achieving the above object, adopt technical scheme as follows:
A preparation method for luffa base cation exchange fibre, comprises the steps:
1) by after air-dry for the luffa of growth and maturity or oven dry, remove epidermis and inner seed, be cut into block luffa;
2) by block luffa boiling water washing, oven dry, be immersed in lucifuge in photosensitizing agent solution and soak, be dipped to volatile matter and volatilize completely; Wherein photosensitizing agent solution be benzophenone be dissolved in volatile organic solvent obtain, concentration is 0.2 ~ 1.0wt%;
3) block for upper step gained luffa is immersed in grafting liquid, carries out graft reaction under UV-irradiation, reacted after washing, acetone extraction, after oven dry, obtain luffa base cation exchange fibre; Wherein grafting liquid is acrylic acid aqueous solution, and concentration is 2.5 ~ 20wt%.
By such scheme, any one of described volatile organic solvent ethanol, methyl alcohol, isopropyl alcohol, acetone.
By such scheme, step 2) in bake out temperature lower than 90 DEG C.
Will ensure the complete submergence luffa of grafting liquid in graft reaction During Illumination of the present invention, reaction can be carried out in air and inert atmosphere, can shorten light application time in inert atmosphere.Ultraviolet source can be high-pressure sodium lamp or hydrogen lamp, xenon lamp, wave-length coverage 200 ~ 400nm.Reacted with boiling water wash residual acrylic monomers, and in apparatus,Soxhlet's with acetone extraction to wash away short chain autopolymer.
Beneficial effect of the present invention is:
The present invention utilizes conventional ultraviolet light elicitation technique, and adopts the method for solution graft copolymerization after first sensitising agent load, simple to operately improves percent grafting; To the mode of acrylic monomers by bonding of functional group be had, and from outward appearance to inner essence be incorporated into natural fiber luffa surface, improve the utilization rate of sensitising agent, grafted monomers.
In the process of ultraviolet lighting, luffa is immersed in acrylic acid aqueous solution, is not only conducive to the infiltration of grafted monomers and base material, and is conducive to the swelling of graft product, thus realizes the useful grafting process of " swollen with grafting solubilising, with swelling short grafting ".
In the present invention, luffa base cation exchange fibre ion exchange capacity is high, to Ce
3+, Cu
2+, Ni
2+358.80mg/g can be reached respectively, 259.78mg/g, 278.54mg/g.
. in the present invention, do not need in the pretreatment process of luffa, with highly basic activation, only to need boiling water to wash, without the need to strictly controlling reaction atmosphere, technique is simple, and equipment is common, is easier to large-scale production; And product specific area is large, exchange rate is fast, and De contamination is simple, commercial Application form is better.
Accompanying drawing explanation
Fig. 1,2: luffa different multiples scanning electron microscope (SEM) photograph before embodiment 2 grafting;
Fig. 3,4: luffa different multiples scanning electron microscope (SEM) photograph after embodiment 2 grafting;
Fig. 5: luffa base cation exchange fibre of the present invention is to the regeneration serviceability of cerium ion.
Detailed description of the invention
Following examples explain technical scheme of the present invention further, but not as limiting the scope of the invention.
The preparation process that the invention provides a kind of luffa base cation exchange fibre is as follows:
By the luffa of self-sow maturation through natural air drying or after drying, cutting, the sponge gourd seed of removing epidermis and pore interior, and be cut into block luffa.
Block luffa is put into boiling water to boil and boil 20 ~ 40min, repeatedly clean away surface impurity with distilled water, dry.
Be placed in the sensitising agent/organic solvent of certain volume by the block luffa of drying, lucifuge is soaked, and is dipped to volatile matter and volatilizees completely.Sensitising agent be benzophenone be dissolved in volatile organic solvent obtain, concentration is 0.2 ~ 1.0wt%.The boiling points such as described volatile organic solvent ethanol, methyl alcohol, isopropyl alcohol, acetone are lower than any one of the organic solvent of 90 DEG C.
Luffa block in step 3 is put into quartz glass reaction still, adds the grafting liquid of certain volume, under UV-irradiation, carry out graft reaction.Reacted with boiling water wash residual acrylic monomers, and in apparatus,Soxhlet's with acetone extraction to wash away short chain autopolymer, namely obtain a kind of luffa base cation exchange fibre after oven dry.Acrylic acid/water solution as grafting liquid, grafting liquid concentration 2.5 ~ 20.0wt%.
Reaction can be carried out in air and inert atmosphere, can shorten light application time in inert atmosphere.Ultraviolet source can be high-pressure sodium lamp or hydrogen lamp, xenon lamp, wave-length coverage 200 ~ 400nm.Reacted with boiling water wash residual acrylic monomers, and in apparatus,Soxhlet's with acetone extraction to wash away short chain autopolymer.
In the present invention, non-woven fabrics percent grafting computing formula is:
wherein p is percent grafting (%), M
xfor the quality (g) after sample graft reaction; M
0for the quality (g) before sample grafting.
Embodiment 1
First by the luffa of self-sow maturation after natural air drying, cutting, removing epidermis and the sponge gourd seed of pore interior, and be cut into block luffa.Block luffa is put into boiling water boil boil 20min after with distilled water washing to remove surface impurity, put into the oven dry of 40 DEG C, baking oven, for subsequent use.Culture dish put into by the above-mentioned block luffa getting certain mass, adds sensitising agent/ethanolic solution that 10ml concentration is 1.0wt%, puts into fume hood lucifuge and soaks; Naturally volatilize completely until photosensitizing agent solution, luffa is transferred in the quartz glass test tube of 40ml, add the acrylic acid/water solution that 20ml concentration is 10.0wt%, use rubber stopper seal test tube, be react 7h under the uviol lamp of 100W at power, reacted the acrylic monomers with its surface of boiling water wash residual, and in apparatus,Soxhlet's with acetone extraction to wash away short chain autopolymer, to weigh after oven dry calculating, the luffa base cation exchange fibre sample that percent grafting is 305.3% can be obtained.
Get the present embodiment luffa base cation exchange fibre 0.025g and be added to the Ce that 25ml concentration is 400mg/g respectively
3+, Cu
2+, Ni
2+in solution, 25 DEG C of vibration 24h in constant temperature oscillator, analytical test obtains it to Ce
3+, Cu
2+, Ni
2+saturated extent of adsorption be respectively 358.80mg/g, 259.78mg/g, 278.54mg/g.
Embodiment 2
First by the luffa of self-sow maturation after natural air drying, cutting, removing epidermis and the sponge gourd seed of pore interior, and be cut into block luffa.Block luffa is put into boiling water boil boil 20min after with distilled water washing to remove surface impurity, put into the oven dry of 40 DEG C, baking oven, for subsequent use.Culture dish put into by the above-mentioned block luffa getting certain mass, adds sensitising agent/methanol solution that 10ml concentration is 0.5wt%, puts into fume hood lucifuge and soaks; Naturally volatilize completely until photosensitizing agent solution, luffa is transferred in the quartz glass test tube of 40ml, add the acrylic acid/water solution that 20ml concentration is 15.0wt%, use rubber stopper seal test tube, be react 48h under the uviol lamp of 7W at power, reacted the acrylic monomers with its surface of boiling water wash residual, and in apparatus,Soxhlet's with acetone extraction to wash away short chain autopolymer, to weigh after oven dry calculating, the luffa base cation exchange fibre sample that percent grafting is 237.4wt% can be obtained.
Before grafting, luffa different multiples scanning electron microscope (SEM) photograph is shown in Fig. 1,2; After grafting, luffa different multiples scanning electron microscope (SEM) photograph is shown in Fig. 3,4.Can obviously find out from figure, after grafting, the surface of luffa becomes smooth, has significantly regular graft, and graft is attached to luffa and substrate surface uniformly.
Embodiment 3
First by the luffa of self-sow maturation after natural air drying, cutting, removing epidermis and the sponge gourd seed of pore interior, and be cut into block luffa.Block luffa is put into boiling water boil boil 20min after with distilled water washing to remove surface impurity, put into the oven dry of 40 DEG C, baking oven, for subsequent use.Culture dish put into by the above-mentioned block luffa getting certain mass, adds sensitising agent/aqueous isopropanol that 10ml concentration is 0.2wt%, puts into fume hood lucifuge and soaks; Naturally volatilize completely until photosensitizing agent solution, luffa is transferred in the quartz glass test tube of 40ml, add the acrylic acid/water solution that 20ml concentration is 20.0wt%, use rubber stopper seal test tube, be react 7h under the uviol lamp of 100W at power, reacted the acrylic monomers with its surface of boiling water wash residual, and in apparatus,Soxhlet's with acetone extraction to wash away short chain autopolymer, to weigh after oven dry calculating, the luffa base cation exchange fibre sample that percent grafting is 254.6% can be obtained.
Embodiment 4
First by the luffa of self-sow maturation after natural air drying, cutting, removing epidermis and the sponge gourd seed of pore interior, and be cut into block luffa.Block luffa is put into boiling water boil boil 20min after with distilled water washing to remove surface impurity, put into the oven dry of 40 DEG C, baking oven, for subsequent use.Culture dish put into by the above-mentioned block luffa getting certain mass, adds sensitising agent/acetone soln that 10ml concentration is 1.0wt%, puts into fume hood lucifuge and soaks; Naturally volatilize completely until photosensitizing agent solution, luffa is transferred in the quartz glass test tube of 40ml, add the acrylic acid/water solution that 20ml concentration is 2.5wt%, use rubber stopper seal test tube, be react 7h under the uviol lamp of 100W at power, reacted the acrylic monomers with its surface of boiling water wash residual, and in apparatus,Soxhlet's with acetone extraction to wash away short chain autopolymer, to weigh after oven dry calculating, the luffa base cation exchange fibre sample that percent grafting is 98.5% can be obtained.
In order to verify De contamination ability of the present invention and power of regeneration, Example 1 gained luffa base cation exchange fibre 0.1g, is added to the Ce that 50ml concentration is 400mg/g
3+in solution, in constant temperature oscillator, 25 DEG C of vibration 24h, analyze and detect it to Ce
3+adsorbance after, be that the HCl solution of 5.0% carries out De contamination experiment to adsorbing saturated sample by 50ml concentration, De contamination test: 25 DEG C of constant temperature oscillators, vibration 24h.After distilled water washing, put into the NaOH solution activation 2h that 5ml concentration is 5.0%, then extremely neutral with distilled water flushing.Repeat absorption and De contamination experiment, experiment acquired results as shown in Figure 5.As can be seen from the figure, during regeneration uses, the absorption property of the luffa base cation exchange material prepared by the method is stablized, and regenerates 10 times, all remains between 320.52mg/g to 358.79mg/g the saturated extent of adsorption of cerium ion.
Claims (3)
1. a preparation method for luffa base cation exchange fibre, is characterized in that comprising the steps:
1) by after air-dry for the luffa of growth and maturity or oven dry, remove epidermis and inner seed, be cut into block luffa;
2) by block luffa boiling water washing, oven dry, be immersed in lucifuge in photosensitizing agent solution and soak, be dipped to volatile matter and volatilize completely; Wherein photosensitizing agent solution is that the molten volatile organic solvent of benzophenone obtains, and concentration is 0.2 ~ 1.0wt%;
3) block for upper step gained luffa is immersed in grafting liquid, carries out graft reaction under UV-irradiation, reacted after washing, acetone extraction, after oven dry, obtain luffa base cation exchange fibre; Wherein grafting liquid is acrylic acid aqueous solution, and concentration is 2.5 ~ 20wt%.
2. the preparation method of luffa base cation exchange fibre as claimed in claim 1, is characterized in that any one of described volatile organic solvent ethanol, methyl alcohol, isopropyl alcohol, acetone.
3. the preparation method of luffa base cation exchange fibre as claimed in claim 1, is characterized in that step 2) in bake out temperature lower than 90 DEG C.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112427018A (en) * | 2020-11-03 | 2021-03-02 | 常州市和润环保科技有限公司 | Heavy metal wastewater biomass adsorbent and preparation method thereof |
| CN112515154A (en) * | 2020-12-08 | 2021-03-19 | 天津科技大学 | Preparation method of functional salt-reduced hericium erinaceus soy sauce and hericium erinaceus soy sauce |
| CN112515110A (en) * | 2020-12-08 | 2021-03-19 | 天津科技大学 | Preparation method of low-tyrosine low-salt flavor soybean paste |
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| JP2003082022A (en) * | 2001-09-07 | 2003-03-19 | Kankyo Eng Co Ltd | Method for producing polymer specifically binding to phenolic compound having endocrine-disrupting action or to its structural analogue and method for separating phenolic compound having endocrine-disrupting action or its structural analogue |
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Patent Citations (2)
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| JP2003082022A (en) * | 2001-09-07 | 2003-03-19 | Kankyo Eng Co Ltd | Method for producing polymer specifically binding to phenolic compound having endocrine-disrupting action or to its structural analogue and method for separating phenolic compound having endocrine-disrupting action or its structural analogue |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112427018A (en) * | 2020-11-03 | 2021-03-02 | 常州市和润环保科技有限公司 | Heavy metal wastewater biomass adsorbent and preparation method thereof |
| CN112515154A (en) * | 2020-12-08 | 2021-03-19 | 天津科技大学 | Preparation method of functional salt-reduced hericium erinaceus soy sauce and hericium erinaceus soy sauce |
| CN112515110A (en) * | 2020-12-08 | 2021-03-19 | 天津科技大学 | Preparation method of low-tyrosine low-salt flavor soybean paste |
| CN112515110B (en) * | 2020-12-08 | 2023-01-10 | 天津科技大学 | Preparation method of low-tyrosine low-salt flavor soybean paste |
| CN112515154B (en) * | 2020-12-08 | 2023-01-10 | 天津科技大学 | Preparation method of functional salt-reduced hericium erinaceus soy sauce and hericium erinaceus soy sauce |
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