CN104624249B - A kind of preparation method of luffa base cation exchange fibre - Google Patents
A kind of preparation method of luffa base cation exchange fibre Download PDFInfo
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- CN104624249B CN104624249B CN201410842847.4A CN201410842847A CN104624249B CN 104624249 B CN104624249 B CN 104624249B CN 201410842847 A CN201410842847 A CN 201410842847A CN 104624249 B CN104624249 B CN 104624249B
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- luffa
- cation exchange
- block
- base cation
- exchange fibre
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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 kind of preparation method of luffa base cation exchange fibre.After the luffa of growth and maturity is air-dried or dried, epidermis and internal seed are removed, block luffa is cut into；Block luffa is washed with boiling water, dried, lucifuge in photosensitizing agent solution is immersed in and soaks, be dipped to volatile matter and volatilize completely；Wherein photosensitizing agent solution is dissolved in volatile organic solvent for benzophenone and is made；Block luffa obtained by upper step is immersed under grafting liquid, ultraviolet light and carries out graft reaction, washing, acetone extraction, obtain luffa base cation exchange fibre after the completion of reaction after drying；Wherein grafting liquid is acrylic acid aqueous solution.Utilize conventional ultraviolet light elicitation technique, and using the method for solution graft copolymerization after first sensitising agent load, acrylic monomers with functional group is introduced natural fiber luffa surface by way of bonding, the utilization rate of grafted monomers is improved, grafting is uniform, adsorption capacity is big and can repeatedly use.
Description
Technical field
The invention belongs to technical field of composite materials, and in particular to a kind of preparation side of luffa base cation exchange fibre
Method.
Background technology
Ion exchange material has in field of industrial waste water treatment such as effluent containing heavy metal ions, dyeing waste waters widely should
With.At present, the chemical products such as the resin/fiber prepared by raw material of non-renewable fossil energy are that in the market is most common,
It is most widely used ion exchange material；Consumption and environmental pollution however as fossil energy it is increasingly serious, utilize day
Right renewable resource, development environment close friend's product and technology are by the inexorable trend as scientific research, therefore development and utilization day
Right biomass-based ion exchange material has very important meaning.In recent years, to rice husk, palm, peanut shell, bagasse and silk
The research that the agriculture and forestry organic waste materials such as melon network are modified adsorbent of the preparation with ion exchanging function is a lot.
Luffa is the plain beam tube of three-dimensional fiber of multidirectional fibrous layer composition in sponge gourd fruit, mainly by cellulose, half
Cellulose and lignin composition.Luffa not only has the features such as yield is high, cheap, degradable and environment-friendly, and its table
Face is porous, and mechanical performance is superior.Therefore, functional graft modification can be carried out to luffa surface, to assign its ion exchangeable
Energy.To luffa carry out graft modification method have a lot, mainly have chemical graft, high-energy radiation be grafted, plasma grafting and
Graft copolymerization etc..Though chemical graft equipment is simple, reaction easily occurs homopolymerization and reaction condition is not easily-controllable once carrying out
System.High-energy radiation and plasma grafting reaction are rapider, and grafting scope can be controlled, but will to the condition and equipment of grafting
Ask higher, and have injury to material main body.Though above grafting method can realize grafting purpose, there is that grafting rate is low, be grafted into
This height, monomer utilization rate it is low, be difficult to realize the common fault produced on a large scale.Comparatively, Graft copolymerization is more easy to realization and connect
Branch purpose, its principle is, by ultraviolet light technology, in the presence of sensitising agent, the macromolecular containing active group to be passed through
The mode of chemical bonding fixes (grafting) can realize the modification performance of material for a long time in substrate surface.Patent CN103223354
A kind of series of steps such as pretreatment, activation, crosslinking, grafting of passing through are disclosed to luffa progress grafting modification, with consumption
When it is short, consume energy less, prepare that cost is low, and the absorption property of product is good, the features such as reclaiming and regenerate simple and convenient.Patent
CN103566907, patent CN104447009 and patent CN103933950 are disclosed with pyromellitic acid anhydride, half Guang ammonia respectively
Acid and solid-loaded ionic-liquid to luffa carry out modification assign its good absorption property, the preferable mechanical performance of product and
Repeat performance, to having preferable adsorption capacity containing heavy metal ion such as chromium, copper, lead, mercury.
The content of the invention
Present invention aims at provide the cation that a kind of simple to operate, grafting is uniform, adsorption capacity is big, can reuse
The preparation method of exchange fiber
It is as follows using technical scheme to reach above-mentioned purpose：
A kind of preparation method of luffa base cation exchange fibre, comprises the following steps：
1) after the luffa of growth and maturity being air-dried or dried, epidermis and internal seed is removed, block luffa is cut into；
2) block luffa is washed with boiling water, dried, be immersed in lucifuge in photosensitizing agent solution and soak, be dipped to volatile matter
Volatilization completely；Wherein photosensitizing agent solution is dissolved in volatile organic solvent for benzophenone and is made, and concentration is 0.2~1.0wt%；
3) block luffa obtained by upper step is immersed under grafting liquid, ultraviolet light and carries out graft reaction, reaction is completed
Washing, acetone extraction, obtain luffa base cation exchange fibre afterwards after drying；Wherein grafting liquid is acrylic acid aqueous solution, dense
Spend for 2.5~20wt%.
By such scheme, the volatile organic solvent ethanol, methanol, isopropanol, acetone any one.
By such scheme, step 2) in drying temperature be less than 90 DEG C.
To ensure that grafting liquid is totally submerged luffa in graft reaction During Illumination of the present invention, reaction can be in air and inertia
Carried out in atmosphere, light application time can be shortened in inert atmosphere.Ultraviolet source can be high-pressure sodium lamp or hydrogen lamp, xenon lamp, wavelength
200~400nm of scope.React completion boiling water wash residual acrylic monomers, and in apparatus,Soxhlet's with acetone extraction with
Wash away short chain autopolymer.
Beneficial effect of the present invention is：
The present invention is using conventional ultraviolet light elicitation technique, and the method for using solution graft copolymerization after first sensitising agent load,
It is simple to operate to improve grafting rate；By the acrylic monomers with functional group by way of bonding, day is from outward appearance to inner essence incorporated into
Right fiber luffa surface, improves the utilization rate of sensitising agent, grafted monomers.
During ultraviolet lighting, luffa is immersed in acrylic acid aqueous solution, not only contributes to grafted monomers and base material
Infiltration, and be conducive to being swelled for graft product, so as to realize the beneficial grafting of " swollen to be grafted solubilising, grafting is promoted to be swelled "
Process.
Luffa base cation exchange fibre ion exchange capacity is high in the present invention, to Ce3+、Cu2+、Ni2+It is reachable respectively
358.80mg/g, 259.78mg/g, 278.54mg/g.
It in the present invention, need not be activated in the pretreatment process of luffa with highly basic, only need boiling water to wash, without
Strict control reaction atmosphere, technique is simple, and equipment is common, it is easier to large-scale production；And product specific surface area is big, exchange rate
It hurry up, De contamination is simple, commercial Application form is preferable.
Brief description of the drawings
Fig. 1,2：Luffa different multiples scanning electron microscope (SEM) photograph before embodiment 2 is grafted；
Fig. 3,4：Luffa different multiples scanning electron microscope (SEM) photograph after embodiment 2 is grafted；
Fig. 5：Regeneration performance of the luffa base cation exchange fibre of the present invention to cerium ion.
Embodiment
Following examples further explain technical scheme, but not as limiting the scope of the invention.
It is as follows that the present invention provides a kind of preparation process of luffa base cation exchange fibre：
By the luffa of natural growth and maturity after natural air drying or drying, cutting removes the silk of epidermis and pore interior
Melon seed, and it is cut into block luffa.
Block luffa is put into boiling in boiling water and boils 20~40min, is cleaned with surface impurity of going out, dried repeatedly with distilled water
It is dry.
The block luffa of drying is placed in sensitising agent/organic solvent of certain volume, lucifuge immersion is dipped to volatilization
Divide volatilization completely.Sensitising agent is dissolved in volatile organic solvent for benzophenone and is made, and concentration is 0.2~1.0wt%.It is described easily to wave
Send out any one of organic solvent of the boiling points such as organic solvent ethanol, methanol, isopropanol, acetone less than 90 DEG C.
Block luffa in step 3 is put into quartz glass reaction kettle, the grafting liquid of certain volume is added, in ultraviolet light
Irradiation is lower to carry out graft reaction.Completion boiling water wash residual acrylic monomers is reacted, and is taken out in apparatus,Soxhlet's with acetone
Carry to wash away short chain autopolymer, a kind of luffa base cation exchange fibre is obtained after drying.Acrylic acid/water solution is as connecing
Branch liquid, 2.5~20.0wt% of grafting liquid concentration.
Reaction can be carried out in air and inert atmosphere, can shorten light application time in inert atmosphere.Ultraviolet source can be with
For high-pressure sodium lamp or hydrogen lamp, xenon lamp, 200~400nm of wave-length coverage.Completion boiling water wash residual acrylic monomers is reacted, and
With acetone extraction to wash away short chain autopolymer in apparatus,Soxhlet's.
Luffa grafting rate calculation formula is in the present invention：Wherein p is grafting rate (%), Mx
For the quality (g) after sample graft reaction；M0Quality (g) before being grafted for sample.
Embodiment 1
First by the luffa of natural growth and maturity after natural air drying, cutting removes the sponge gourd kind of epidermis and pore interior
Son, and it is cut into block luffa.Block luffa is put into boiling in boiling water and boils miscellaneous to remove surface with distillation water washing after 20min
Matter, is put into 40 DEG C of drying in baking oven, standby.Take the above-mentioned block luffa of certain mass to be put into culture dish, add 10ml dense
Sensitising agent/ethanol solution for 1.0wt% is spent, lucifuge in fume hood is put into and soaks；After photosensitizing agent solution volatilizees completely naturally,
Luffa is transferred in 40ml quartz glass test tube, the acrylic acid/water solution that 20ml concentration is 10.0wt% is added, uses rubber
Plug seals test tube, and 7h, the propylene on reaction completion its surface of boiling water wash residual are reacted in the case where power is 100W uviol lamp
Acid monomers, and in apparatus,Soxhlet's with acetone extraction to wash away calculating of being weighed after short chain autopolymer, drying, you can be grafted
Rate is 305.3% luffa base cation exchange fibre sample.
It is 400mg/g's to take the present embodiment luffa base cation exchange fibre 0.025g to be added to 25ml concentration respectively
Ce3+、Cu2+、Ni2+In solution, in constant temperature oscillator 25 DEG C vibration 24h, analysis test its to Ce3+、Cu2+、Ni2+Saturation
Adsorbance is respectively 358.80mg/g, 259.78mg/g, 278.54mg/g.
Embodiment 2
First by the luffa of natural growth and maturity after natural air drying, cutting removes the sponge gourd kind of epidermis and pore interior
Son, and it is cut into block luffa.Block luffa is put into boiling in boiling water and boils miscellaneous to remove surface with distillation water washing after 20min
Matter, is put into 40 DEG C of drying in baking oven, standby.Take the above-mentioned block luffa of certain mass to be put into culture dish, add 10ml dense
Sensitising agent/methanol solution for 0.5wt% is spent, lucifuge in fume hood is put into and soaks；After photosensitizing agent solution volatilizees completely naturally,
Luffa is transferred in 40ml quartz glass test tube, the acrylic acid/water solution that 20ml concentration is 15.0wt% is added, uses rubber
Plug seals test tube, and 48h, the acrylic acid on reaction completion its surface of boiling water wash residual are reacted in the case where power is 7W uviol lamp
Monomer, and in apparatus,Soxhlet's with acetone extraction to wash away calculating of being weighed after short chain autopolymer, drying, grafting rate can be obtained
For 237.4wt% luffa base cation exchange fibre sample.
Luffa different multiples scanning electron microscope (SEM) photograph is shown in Fig. 1,2 before grafting；Luffa different multiples scanning electron microscope (SEM) photograph after grafting
See Fig. 3,4.From the graph, it is apparent that the surface of luffa becomes smooth after grafting, there is obvious regular graft, and
Graft is uniformly adhered to luffa and substrate surface.
Embodiment 3
First by the luffa of natural growth and maturity after natural air drying, cutting removes the sponge gourd kind of epidermis and pore interior
Son, and it is cut into block luffa.Block luffa is put into boiling in boiling water and boils miscellaneous to remove surface with distillation water washing after 20min
Matter, is put into 40 DEG C of drying in baking oven, standby.Take the above-mentioned block luffa of certain mass to be put into culture dish, add 10ml dense
Sensitising agent/aqueous isopropanol for 0.2wt% is spent, lucifuge in fume hood is put into and soaks；Treat that photosensitizing agent solution volatilizees completely naturally
Afterwards, luffa is transferred in 40ml quartz glass test tube, adds the acrylic acid/water solution that 20ml concentration is 20.0wt%,
Rubber stopper seal test tube is used, 7h, reaction completion its surface of boiling water wash residual are reacted in the case where power is 100W uviol lamp
Acrylic monomers, and in apparatus,Soxhlet's with acetone extraction to wash away calculating of being weighed after short chain autopolymer, drying, you can obtain
Grafting rate is 254.6% luffa base cation exchange fibre sample.
Embodiment 4
First by the luffa of natural growth and maturity after natural air drying, cutting removes the sponge gourd kind of epidermis and pore interior
Son, and it is cut into block luffa.Block luffa is put into boiling in boiling water and boils miscellaneous to remove surface with distillation water washing after 20min
Matter, is put into 40 DEG C of drying in baking oven, standby.Take the above-mentioned block luffa of certain mass to be put into culture dish, add 10ml dense
Sensitising agent/acetone soln for 1.0wt% is spent, lucifuge in fume hood is put into and soaks；After photosensitizing agent solution volatilizees completely naturally,
Luffa is transferred in 40ml quartz glass test tube, the acrylic acid/water solution that 20ml concentration is 2.5wt% is added, uses rubber
Plug seals test tube, and 7h, the propylene on reaction completion its surface of boiling water wash residual are reacted in the case where power is 100W uviol lamp
Acid monomers, and in apparatus,Soxhlet's with acetone extraction to wash away calculating of being weighed after short chain autopolymer, drying, you can be grafted
Rate is 98.5% luffa base cation exchange fibre sample.
In order to verify De contamination ability of the present invention and power of regeneration, the gained luffa base cation exchange of Example 1 is fine
0.1g is tieed up, the Ce that 50ml concentration is 400mg/g is added to3+In solution, 25 DEG C of vibration 24h in constant temperature oscillator, analysis detection
It is to Ce3+Adsorbance after, De contamination experiment is carried out to the sample of adsorption saturation for 5.0% HCl solution with 50ml concentration,
De contamination is tested：25 DEG C of constant temperature oscillators, vibrate 24h.After distillation water washing, the NaOH solution that 5ml concentration is 5.0% is put into
2h is activated, then with distilled water flushing to neutrality.Repeat absorption and De contamination experiment, experiment acquired results are as shown in Figure 5.
It can be seen that the absorption property stabilization in use, the luffa base cation exchange material prepared by this method is regenerated,
Regeneration 10 times, 320.52mg/g is held between 358.79mg/g to the saturated extent of adsorption of cerium ion.
Claims (3)
1. a kind of preparation method of luffa base cation exchange fibre, it is characterised in that comprise the following steps：
1) after the luffa of growth and maturity being air-dried or dried, epidermis and internal seed is removed, block luffa is cut into；
2) block luffa is washed with boiling water, dried, be immersed in lucifuge in photosensitizing agent solution and soak, be dipped to volatile matter complete
Volatilization；Wherein photosensitizing agent solution is dissolved in volatile organic solvent for benzophenone and is made, and concentration is 0.2~1.0wt%；
3) block luffa obtained by upper step is immersed under grafting liquid, ultraviolet light and carries out graft reaction, water after the completion of reaction
Wash, acetone extraction, luffa base cation exchange fibre is obtained after drying；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, it is characterised in that the volatility has
Any one of machine etoh solvent, methanol, isopropanol, acetone.
3. the preparation method of luffa base cation exchange fibre as claimed in claim 1, it is characterised in that step 2) in baking
Dry temperature is less than 90 DEG C.
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