CN102614852B - Preparation method for spongy ion exchange fiber - Google Patents
Preparation method for spongy ion exchange fiber Download PDFInfo
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Abstract
The invention relates to a method for preparing natural plant ion exchange fiber with an agricultural product of vegetable sponge. The preparation method for spongy ion exchange fiber is characterized by including the following steps: 1 after natural withering or drying, mature plant fruit of luffa after normal growth is cut to be a cylindrical body as long as 5cm to 15cm, skin and seeds inside gaps of the luffa are removed to obtain the cylindrical vegetable sponge; 2 the prepared cylindrical vegetable sponge is pretreated with one of the methods in attached diagrams; 3 activating; 4 catalyzing; 5 stem grafting; and 6 cleaning, drying, and obtaining the spongy ion exchange fiber. Compared with the existing preparation method of ion exchange fiber, the method for preparing natural plant ion exchange fiber with the agricultural product of vegetable sponge is simple, clear, short in consumed time, little in consumed energy, low in preparation cost, good in product absorptive property, simple and convenient in recovery and regeneration, and especially suitable for industrial popularization.
Description
Technical field
The present invention relates to a kind of preparation method of spongy ion-exchange fibre, particularly a kind of method of utilizing the agricultural products luffa to prepare the natural plants ion-exchange fibre.
Background technology
ion-exchange fibre (ion exchange fibers, IEF) be adsorption and the parting material of a fibre-like, main surface active groups by fiber or fibrous polymer exchanges from the exchangeable ion that solves and some same sex ion, with traditional Ion Exchange Resin Phase ratio, it is large that IEF has specific area, chemical stability is higher, the mass transfer distance is short, sorption and desorption speed is fast, adsorptive selectivity is strong (to metal ion, organic molecule, pernicious gases etc. have higher adsorptive selectivity), purify thoroughly, wash-out and power of regeneration are strong, energy consumption is low, the plurality of advantages such as the little and biologically active of fluid resistance is high.The fields such as the separation and acquisition of recycling, medicine of isolation of purified, the precious metal ion of water treatment, gas and biochemical industry now have been widely used in, it is Developing new high-tech industry rapidly, along with constantly bringing forth new ideas and progress of preparation method, the application prospect of IEF is more wide.
In addition, ion-exchange fibre also has the various informative special feature of Application and Development, can make the forms such as fiber, short fiber, fabric, non-weaving cloth, felt, net, therefore can be applicable to the ion exchange process of various different conditions.CN 1262706C has reported a kind of ion-exchange fibre and fabric thereof the preparation method in closed reactor, its fabric product has ability and the power of regeneration of superpower absorption pernicious gas (sulfur dioxide, ammonia, hydrogen fluoride, hydrogen chloride), has good economic and social profit.CN 101736525 A have announced a kind of method of the non-weaving cloth by the ion-exchange fibre preparation, this non-woven cotton material is applied in the absorbent device of super absorbent polymer, can greatly improve the water absorbent rate of super absorbent polymer, and then the use amount of super absorbent polymer in the minimizing absorbent device, economic benefit and actual benefit obviously improve.CN 101036897A discloses the method for utilizing crop waste fiber rice straw, maize straw, useless flax silk, waste cotton to prepare anionite, and its preparation technology is simple, and cost of material is cheap, is particularly suitable for processing anion-containing waste water.
For the research of ion-exchange fibre, be study hotspot in west American-European countries, Japan, the former Soviet Union, had many research report and achievement.Wherein Japan and former Soviet Union research morning and study more, the product that has formed seriations such as comprising anion, cation, both sexes, chelating such as TIN and Muscovite VION, the FIBAN etc. of Japan.In RU1658444, prepared the Fibriform adsorbents that contains carboxyl and diazanyl, the ammonia in gas and ammonium nitrate there are is higher purification efficiency.At home, the seventies beginning has been launched development and the application work of ion exchange fiber material, the mechanisms such as Zhongshan University, Beijing Institute of Technology, Henan fine chemistry industry key lab, Beijing Institute of Clothing Tech have successively developed multiple different ion exchange fiber material, and the practical application of some products are arranged in each different field.Related to a kind of method that adopts sweller and free radical protective agent to produce ion-exchange fibre as CN 1112257C, its product exchange capacity is up to 3.0～5.0 mMs of every grams, and cost is low, long service life and environmentally safe.
Utilize at present natural plants raw material or composite fibre materials to prepare the main technique method of ion-exchange fibre and above-mentioned process or identical or Combined Mining use or further improvement on these method bases.Wherein utilize raw material that the natural plants raw material prepare natural plants base ion-exchange fibre just like agricultural product, agricultural byproducts, agricultural wastes, other plant etc., such as stalk, rice husk, pericarp, linen-cotton etc.Their key component is cellulose, also contains hemicellulose, lignin and pectin.
In actual applications, though preparation keeps the technique simplicity of the ion-exchange fibre of complete physical structure, but the utilization ratio of its exchange capacity and product is lower than graininess ion-exchanger and Powdered ion exchange material, industrial applications exists certain restricted, further reduces the research and development preparation cost and further improves the service efficiency of product and the developing direction that is ion-exchange fibre service life.
Sponge gourd (Luffa cylindria) has another name called day sieve wadding, day network and becomes melon etc., belongs to annual Curcurbitaceae and climbs up by holding on to vegetation.Sponge gourd divides general sponge gourd (Luffa cylindvica Roem) and rib sponge gourd (Luffa acutangula Roxb) is arranged, originate in India, be distributed widely in the torrid zone, subtropical zone and the Temperate Region in China in Asia, sponge gourd is one of vegetables in summer, therefore in China's Jiangsu-zhejiang Shanghai Area and Guangdong, the Guangxi plantation is very general.Generally use tender melon as dish use, do the tasty and refreshing deliciousness of soup taste.Luffa (Vegetable Sponge of Luffa) has another name called sponge gourd net, day sieve line, day sieve muscle etc., it is the three-dimensional fiber tube bank that skin thick in the fruit after the sponge gourd maturation and multidirectional fibrage form, three major polymers: cellulose, hemicellulose and lignin form, and its content of cellulose is up to more than 60%.At present, the research of luffa mainly concentrates on its medical value and prepares shower used in everyday, bath accessory.Compendium of Material Medica is put down in writing it can lead to people's train of thought internal organs, and goes the wind detoxifcation, and detumescence is reduced phlegm, and Eradicates pain desinsection is controlled all blood sick.Aspect the routine use article, existing multinomial invention, as luffa soap, luffa mattress, Luffa sponge cleaning brush, Loofah insole etc.
As from the foregoing, at present all also more original to processing and the treatment technology of luffa, mostly utilized its natural vascular structure.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of spongy ion-exchange fibre, the method has the advantages that cost is low, absorption property is good.
For achieving the above object, the technical solution used in the present invention is: a kind of preparation method of spongy ion-exchange fibre is characterized in that it comprises the steps:
1) the vegetable silk melon and fruit after the normal growth maturation is real, after natural air drying or oven dry, cut into the long cylinder of 5～15cm, remove the sponge gourd seed of epidermis and hole inside, obtain cylinder luffa [the string vascular bundle cylinder (strong but pliable in texture) that inside interweaves and is netted];
2) the cylinder luffa that will get ready carries out pretreatment with one of following two kinds of methods:
A) it is the rectangular-shaped of 0.5cm*0.5cm*0.5cm to 1cm*1cm*1cm that the cylinder luffa that will get ready is cut into the high scope of the wide * of long *, obtains rectangular-shaped luffa (being the luffa fritter); Rectangular-shaped luffa is dipped in distilled water and stirs 1～2h, then luffa is dried 12h in 60～65 ℃ of baking ovens, obtain the dried loofah of fritter;
B) it is highly the small cylinder of 3～7cm that the cylinder luffa that will get ready is sawn into, and obtains the luffa of small cylinder; The luffa of small cylinder is soaked 8～12h in distilled water; Then be placed in 60～65 ℃ of baking ovens and dry 12h, obtain the dried loofah of fritter;
3) activation: the dried loofah of weighing 1～3g fritter, the dried loofah of fritter is placed in the mixed solution of 80～120ml DMF (DMF) and 20-80ml epoxychloropropane, stir 0.5～2h under 70～100 ℃ of condition of water bath heating;
4) catalysis: add 10～40ml pyridine solution to make catalyst, continue 70～100 ℃ of heating water bath 0.5～2h;
5) grafting: add 20～40ml dimethylamine (DMA) (concentration is 33wt%) aqueous solution, continue 70～100 ℃ of heating water bath 2～4h, obtain the luffa (preliminary product) after grafting;
6) clean:
A) with the luffa after grafting cooling (being cooled to below 20 ℃), the NaOH solution drip washing of use 0.1mol/L 2～3 times, then insert 500ml
,0.1mol/L NaOH solution in, bathe heating and strong stirring 5～10min(removes ash content, residue, part polysaccharide material at 30～40 ℃ of Water Unders);
B) with above-mentioned steps 6) a) resulting luffa 0.1mol/LHCl solution drip washing 2～3 times, then insert 500ml
,0.1mol/LHCl in solution, at 30～40 ℃ of Water Unders, bathe heating and strong stirring 5～10min, regulate pH to neutral;
C) with above-mentioned steps 6) b) resulting luffa is the ethanolic solution drip washing 2～3 times of 50wt% with concentration, then inserts 500ml
,Concentration is in the ethanolic solution of 50wt%, at 30～40 ℃ of Water Unders, bathes heating and the residual organic reactant of strong stirring 5～10min(removal);
D) with above-mentioned steps 6) c) 0.1mol/LNaCl aqueous solution drip washing 2～3 times of resulting luffa, then insert 500ml
,0.1mol/LNaCl in the aqueous solution, at 30～40 ℃ of Water Unders, bathe heating and strong stirring 5～10min, the luffa after being cleaned;
7) luffa after cleaning, in dry 12h under 60～65 ℃ of conditions, obtains spongy ion-exchange fibre (final products, sealing is stored in drier, and is standby).
Described strong stirring refers to that speed of agitator is 200～300r/min.
Utilize the mode that heating water bath electric stirring or heating water bath and magnetic agitation are carried out simultaneously to clean and take off slag product.In lessivation, glass apparatus sand core funnel or filter funnel have been utilized, first-selected sand core funnel.
Plantation quantity at China's sponge gourd is huge, therefore utilize luffa to prepare ion-exchange fibre for raw material exploitation, compare with technology with existing ion-exchange fibre raw materials, the characteristics that possess cost low (economy), facility and environmental protection (cleaning), all be significant for the means, approach and the novelty that improve China's ion-exchange fibre preparation.
The invention has the beneficial effects as follows: take the product sponge gourd ripening fruits of crops as raw material, prepare the natural plants ion-exchange fibre, opened up the kind of natural plants ion-exchange fibre raw materials and prepared approach, compare with the approach for preparing of existing ion-exchange fibre, preparation technology is simple and clear, and is consuming time short, and power consumption is few, preparation cost is low, absorption property is good, reclaims and regenerates simple and conveniently, is particularly suitable for industry and promotes.
Description of drawings
Fig. 1 is process chart of the present invention.
Fig. 2 is that the embodiment of the present invention 1 obtains the absorption figure of spongy ion-exchange fibre to nitrate ion.
Fig. 3 is that the embodiment of the present invention 1 obtains spongy ion-exchange fibre regeneration tests curve map.
The specific embodiment
, in order to understand better the present invention, further describe content of the present invention below in conjunction with specific embodiment, but content of the present invention not only is confined to the following examples.
Embodiment 1:
As shown in Figure 1, a kind of preparation method of spongy ion-exchange fibre, it comprises the steps:
1) the vegetable silk melon and fruit after the normal growth maturation is real, after natural air drying or oven dry, cut into the long cylinder of 5～15cm, remove the sponge gourd seed of epidermis and hole inside, obtain cylinder luffa [the string vascular bundle cylinder (strong but pliable in texture) that inside interweaves and is netted];
2) the cylinder luffa that will get ready carries out pretreatment: the structure that is cut into a large amount of similar little cuboids with the cylindrical shape luffa that clean scissors will be got ready, the scope that the wide * of long * is high is 0.5cm*0.5cm*0.5cm to 1cm*1cm*1cm, obtains rectangular-shaped luffa (being the luffa fritter); The rectangular-shaped luffa that shears is put into the beaker of the 10L that cleaned with distilled water, poured into distilled water 6～8L, soak, stir with electric mixer simultaneously, make the luffa fritter fully mix and contact with distilled water; Soak and stir 1～2h, then the luffa fritter being poured in clean screen cloth, related screen cloth is put into baking oven at 60～65 ℃ of oven dry 12h, obtains the dried loofah of fritter;
3) activation: take out above dried loofah from baking oven, the dried loofah of weighing 1g fritter, put into the flask with three necks,round bottom of 1L, two side mouths of there-necked flask cover and (annotate: uncap when needs add medicine only with glass cover, continue to cover after adding medicine, all so operations in whole course of reaction), stretch into electric mixer from there-necked flask master mouth, add 80ml N from there-necked flask side mouth with little glass funnel, dinethylformamide (DMF) solution, 50ml epoxychloropropane solution, the unlatching electric stirring continues to be uniformly mixed solution and (makes the abundant haptoreaction of luffa and reagent, rotating speed is at 60～100r/min, stir and do not stop in whole course of reaction) bathe heating 0.5～1h at 85 ℃ of Water Unders,
4) catalysis: add the 10ml pyridine solution to make catalyst, at 100 ℃ of Water Unders, bathe heating 1h;
5) grafting: add 30ml dimethylamine (DMA) (concentration the is 33wt%) aqueous solution, continue 100 ℃ of heating water bath 3h, obtain the luffa (preliminary product) after grafting;
6) clean:
A) (preliminary product is poured out from there-necked flask to clean screen cloth the luffa after grafting is cooling, be cooled to below 20 ℃, transfer in sand core funnel), with the NaOH solution drip washing of 0.5～1L, 0.1mol/L 2～3 times, then luffa is transferred in the 500ml large beaker, pours 500ml into
,0.1mol/L NaOH solution in, bathe heating and strong stirring 5～10min(removes ash content, residue, part polysaccharide material at 30 ℃ of Water Unders, described strong stirring refers to that speed of agitator is 200～300r/min, below identical);
B) with above-mentioned steps 6) a) resulting luffa 0.1mol/LHCl solution drip washing 2～3 times, then luffa is transferred in the 500ml large beaker, pour 500ml into
,0.1mol/LHCl in solution, at 30 ℃ of Water Unders, bathe heating and strong stirring 5～10min, regulate pH to neutral;
C) with above-mentioned steps 6) b) resulting luffa is the ethanolic solution drip washing 2～3 times of 50wt% with concentration, then luffa is transferred in the 500ml large beaker, pours 500ml into
,Concentration is in the ethanolic solution of 50wt%, at 30～40 ℃ of Water Unders, bathes heating and the residual organic reactant of strong stirring 5～10min(removal);
D) with above-mentioned steps 6) c) 0.1mol/LNaCl aqueous solution drip washing 2～3 times of resulting luffa, then luffa is transferred in the 500ml large beaker, pour 500ml into
,0.1mol/LNaCl in the aqueous solution, at 30～40 ℃ of Water Unders, bathe heating and strong stirring 5～10min, the luffa after obtaining (purpose is thorough wash off product);
7) luffa after cleaning goes to screen cloth, dries 12h under 60～65 ℃ of conditions, obtains spongy ion-exchange fibre (final products, sealing is stored in drier, and is standby).
, for performance and the effect that shows better this spongy ion-exchange fibre, with it, nitrate ion in water is inhaled
The test of attached performance, concrete experimental technique is as follows:
Take many parts of 0.1g embodiment 1 products obtained therefroms, put into respectively the iodine flask of clean 250ml, pour 50ml 50mg/L into
The KNO of (referring to nitrate concentration)
3The aqueous solution, build lid, and in the lower vibration of temperature (20 ± 1 ℃), oscillation intensity is 120r/min, vibration 60min.Nitrate ion concentration is measured with the nitrate determination method shown in GBT 8538-1995, and the related experiment result as table 1(figure as shown in Figure 2).
Can obtain after product contact solution and be adsorbed as quick adsorption in 30 minutes by absorption-time graph, this stage through the spongy physics structure of product hold back, adhere to and functional group's tertiary amine group of grafting to the absorption of nitrate ion, nitrate ion in can the fast processing aqueous solution, haptoreaction 60min can reach the maximum adsorption clearance.
The impact of table 1 product dosage on clearance:
| Product dosage (g) | Nitrate anion clearance (%) |
| 0.05 | 75.10 |
| 0.1 | 90.04 |
| 0.15 | 94.93 |
| 0.2 | 100 |
Embodiment 2:
A kind of preparation method of spongy ion-exchange fibre, it comprises the steps:
1) the vegetable silk melon and fruit after the normal growth maturation is real, after natural air drying or oven dry, cut into the long cylinder of 5～15cm, remove the sponge gourd seed of epidermis and hole inside, obtain cylinder luffa [the string vascular bundle cylinder (strong but pliable in texture) that inside interweaves and is netted];
2) the cylinder luffa that will get ready carries out pretreatment: the structure that is cut into a large amount of similar little cuboids with the cylindrical shape luffa that clean scissors will be got ready, the scope that the wide * of long * is high is 0.5cm*0.5cm*0.5cm to 1cm*1cm*1cm, the fritter that shears is put into the beaker of the 10L that cleaned with distilled water, pour distilled water 6～8L into, soak, stir with electric mixer simultaneously, make the luffa fritter fully mix and contact with distilled water; Soak and stir 1～2h, then the luffa fritter being poured in clean screen cloth, related screen cloth is put into baking oven at 60～65 ℃ of oven dry 12h, obtains the dried loofah of fritter;
3) activation: the dried loofah of weighing 2g fritter, put into the flask with three necks,round bottom of 1L, two side mouths of there-necked flask cover and (annotate: uncap when needs add medicine only with glass cover, continue to cover after adding medicine, all so operations in whole course of reaction), stretch into electric mixer from there-necked flask master mouth, add 120ml N from there-necked flask side mouth with little glass funnel, dinethylformamide (DMF) solution, 80ml epoxychloropropane solution, the unlatching electric stirring continues to be uniformly mixed solution and (makes the abundant haptoreaction of luffa and reagent, rotating speed is at 60～100r/min, stir and do not stop in whole course of reaction) bathe heating 1h at 100 ℃ of Water Unders,
4) catalysis: add the 10ml pyridine solution to make catalyst, at 100 ℃ of Water Unders, bathe heating 1h;
5) grafting: add dimethylamine (DMA) aqueous solution of 30ml 33 wt %, at 100 ℃ of Water Unders, bathe heating 3h, obtain the luffa (preliminary product) after grafting;
6) clean:
A) luffa after grafting (preliminary product) is poured out to clean screen cloth from there-necked flask, be cooled to below 20 ℃, transfer in sand core funnel, with the NaOH solution drip washing of 1L0.1mol/L 2～3 times, then with transferred product to the 500ml large beaker, pour the NaOH solution of 500ml0.1mol/L into, 40 ℃ of heating water baths also decolour and get rid of and take off residue in hole with the electric mixer strong stirring, agitator speed 200～300r/min, duration min.Cleaning purpose with NaOH is to remove ash content, residue, part polysaccharide material;
B) with above-mentioned steps 6) a) resulting luffa 0.1mol/LHCl solution drip washing 2～3 times, then insert 500ml
,, 0.1mol/LHCl in solution, in 30～40 ℃ of Water Unders bath heating and strong stirring 5～10min(speed of agitator, be 200～300r/min), regulate pH to neutrality;
C) with above-mentioned steps 6) b) resulting luffa is the ethanolic solution drip washing 2～3 times of 50wt% with concentration, then inserts 500ml
,Concentration is in the ethanolic solution of 50wt%, in 30～40 ℃ of Water Unders bath heating and strong stirring 5～10min(speed of agitator, is 200～300r/min, removes residual organic reactant);
D) with above-mentioned steps 6) c) 0.1mol/LNaCl aqueous solution drip washing 2～3 times of resulting luffa, then insert 500ml
,0.1mol/LNaCl in the aqueous solution, in 30～40 ℃ of Water Unders bath heating and strong stirring 5～10min(speed of agitator, be 200～300r/min), the luffa product after being cleaned;
7) the luffa product after cleaning goes to screen cloth, dries 12h under 60～65 ℃ of conditions, obtains spongy ion-exchange fibre (final products, sealing is stored in drying box, and is standby).
Table 2
| Product dosage (g) | Nitrate anion clearance (%) |
| 0.05 | 80.02 |
| 0.1 | 90.30 |
| 0.15 | 95.76 |
| 0.2 | 100 |
Embodiment 3:
A kind of preparation method of spongy ion-exchange fibre, it comprises the steps:
1) the vegetable silk melon and fruit after the normal growth maturation is real, after natural air drying or oven dry, cut into the long cylinder of 5～15cm, remove the sponge gourd seed of epidermis and hole inside, obtain cylinder luffa [the string vascular bundle cylinder (strong but pliable in texture) that inside interweaves and is netted];
2) the cylinder luffa that will get ready carries out pretreatment: the structure that is cut into a large amount of similar little cuboids with the cylindrical shape luffa that clean scissors will be got ready, the scope that the wide * of long * is high is 0.5cm*0.5cm*0.5cm to 1cm*1cm*1cm, the fritter that shears is put into the beaker of the 10L that cleaned with distilled water, pour distilled water 6～8L into, soak, stir with electric mixer simultaneously, make the luffa fritter fully mix and contact with distilled water.Soak and stir 1～2h, then the luffa fritter being poured in clean screen cloth, related screen cloth is put into baking oven at 60～65 ℃ of oven dry 12h, obtains the dried loofah of fritter;
3) activation: take out above Raw (dried loofah of fritter) from baking oven, the dried loofah (luffa fritter) of accurate weighing 3g fritter, put into the flask with three necks,round bottom of 1L, two side mouths of there-necked flask cover and (annotate: uncap when needs add medicine only with glass cover, continue to cover after adding medicine, all so operations in whole course of reaction), stretch into electric mixer from there-necked flask master mouth; Add 120ml N from there-necked flask side mouth with little glass funnel, dinethylformamide (DMF) solution, 80ml epoxychloropropane solution, the unlatching electric stirring continues to be uniformly mixed solution and (makes the abundant haptoreaction of luffa and reagent, rotating speed, at 60～100r/min, stirs and does not stop in whole course of reaction) bathe heating 1h at 100 ℃ of Water Unders;
4) catalysis: add the 20ml pyridine solution to make catalyst, at 100 ℃ of Water Unders, bathe heating 1h;
5) grafting: adding 40ml(concentration is 33wt%) dimethylamine (DMA) aqueous solution, bathe heating 3h at 100 ℃ of Water Unders, obtain the luffa (preliminary product) after grafting;
6) clean: a) preliminary product is poured out from there-necked flask to clean screen cloth, be cooled to below 20 ℃, transfer in sand core funnel, with the NaOH solution drip washing of 1L0.1mol/L 2～3 times, then preliminary product is transferred in the 500ml large beaker, pours the NaOH solution of 500ml0.1mol/L into, 30 ℃ of heating water baths also decolour and get rid of and take off residue in hole with the electric mixer strong stirring, agitator speed 200～300r/min, duration 5～10min.Cleaning purpose with NaOH is to remove ash content, residue, part polysaccharide material;
B) with above-mentioned steps 6) a) resulting luffa 0.1mol/LHCl solution drip washing 2～3 times, then insert 500ml
,0.1mol/LHCl in solution, at 30～40 ℃ of Water Unders, bathe heating and strong stirring 5～10min(agitator magnetic stirring apparatus, agitator speed 200～300r/min), regulate pH to neutral;
C) with above-mentioned steps 6) b) resulting luffa is the ethanolic solution drip washing 2～3 times of 50wt% with concentration, then inserts 500ml
,Concentration is in the ethanolic solution of 50wt%, at 30～40 ℃ of Water Unders, bathes heating and strong stirring 5～10min(agitator speed 200～300r/min, removes residual organic reactant);
D) with above-mentioned steps 6) c) 0.1mol/LNaCl aqueous solution drip washing 2～3 times of resulting luffa, then insert 500ml
,0.1mol/LNaCl in the aqueous solution, at 30～40 ℃ of Water Unders, bathe heating and strong stirring 5～10min, the luffa after obtaining;
7) luffa after cleaning changes sand core funnel over to, and the luffa after cleaning, in dry 12h under 60～65 ℃ of conditions, is obtained spongy ion-exchange fibre (final products, sealing is stored in drying box, and is standby).
The experimental technique experiment condition of embodiment 3 eliminating rate of absorption is with embodiment 1, and result is identical with embodiment 1.
In order better to show the performance of this spongy ion-exchange fibre, the saturated product of absorption of embodiment 1, embodiment 2, embodiment 3 to be regenerated-adsorption experiment, experimental technique and result are as follows:
Get the saturated product of absorption of the 0.1g of equivalent, with a small amount of 0.1mol/LNaCl solution drip washing 2～3 times, be transferred to the common centrifuge tube of 50ml, the NaOH solution that adds the 0.1mol/L of 30ml, in centrifuge after centrifugal 30min, then 0.1mol/LNaCl solution drip washing 2～3 times, washed with de-ionized water 2 times, dry 12h under 60 ℃, re-start absorption and desorption experiment, acquired results such as Fig. 3.
Experiment condition: 50ml 50mg/L(refers to nitrate concentration) KNO
3The aqueous solution; Spongy exchange fiber dosage 0.1g;
20 ± 1 ℃ of temperature; Vibration rotating speed 120r/min; Duration of oscillation 60min.
Product is long life cycle as can be known by the exchange regeneration tests, and adsorption capacity reduces slower, there is no obvious downward trend, tests only 0.1g reconstituted product to ten secondaries and still can keep 77.5% clearance to the nitrate ion of experimental solutions.
Embodiment 4: substantially the same manner as Example 2, difference is that the bath temperature of three reactions steps is followed successively by: 85 ℃, 100 ℃, 85 ℃.
The experimental technique experiment condition of eliminating rate of absorption is with embodiment 2, and result is identical with embodiment 2.
Regeneration tests is with embodiment 1, and result is identical with embodiment 1.
Embodiment 5: substantially the same manner as Example 2, difference is that the NaCl solution of the 0.1mol/L in last cleaning products stage replaces with deionized water.
The experimental technique experiment condition of eliminating rate of absorption is with embodiment 2, and result is identical with embodiment 2.
Regeneration tests is with embodiment 1, and result is identical with embodiment 1.
Embodiment 6: substantially the same manner as Example 2, what difference was that raw material uses is complete small cylinder shape luffa. the reaction drug dosage is (small cylinder shape luffa quality/2g) multiply by.There-necked flask replaces with the bigbore beaker of 1L, but with the magnetic stirring apparatus of temperature control, adds thermal agitation.
The experimental technique experiment condition of eliminating rate of absorption is with embodiment 2, and result is identical with embodiment 2.
Regeneration tests is with embodiment 1, and result is identical with embodiment 1.
Embodiment 7: substantially the same manner as Example 2, difference is: the cylinder luffa that 2) will get ready carries out pretreatment: it is highly the small cylinder of 3～7cm that the cylinder luffa that will get ready is sawn into, and obtains the luffa of small cylinder; The luffa of small cylinder is soaked 8～12h in distilled water; Then be placed in 60～65 ℃ of baking ovens and dry 12h, obtain the dried loofah of fritter.
The experimental technique experiment condition of eliminating rate of absorption is with embodiment 2, and result is identical with embodiment 2.
Regeneration tests is with embodiment 1, and result is identical with embodiment 1.
Embodiment 8: substantially the same manner as Example 2, difference is: catalysis: add the 40ml pyridine solution to make catalyst, continue 70 ℃ of heating water baths 0.5.
The experimental technique experiment condition of eliminating rate of absorption is with embodiment 2, and result is identical with embodiment 2.
Regeneration tests is with embodiment 1, and result is identical with embodiment 1.
Embodiment 9: substantially the same manner as Example 2, difference is: catalysis: add the 40ml pyridine solution to make catalyst, continue 70 ℃ of heating water bath 2h.
The experimental technique experiment condition of eliminating rate of absorption is with embodiment 2, and result is identical with embodiment 2.
Regeneration tests is with embodiment 1, and result is identical with embodiment 1.
Embodiment 10: substantially the same manner as Example 2, difference is: grafting: add 20ml dimethylamine (DMA) (concentration the is 33wt%) aqueous solution, continue 70 ℃ of heating water bath 2h, obtain the luffa (preliminary product) after grafting.
The experimental technique experiment condition of eliminating rate of absorption is with embodiment 2, and result is identical with embodiment 2.
Regeneration tests is with embodiment 1, and result is identical with embodiment 1.
Embodiment 11: substantially the same manner as Example 2, difference is: grafting: add 20ml dimethylamine (DMA) (concentration the is 33wt%) aqueous solution, continue 70 ℃ of heating water bath 4h, obtain the luffa (preliminary product) after grafting.
The experimental technique experiment condition of eliminating rate of absorption is with embodiment 2, and result is identical with embodiment 2.
Regeneration tests is with embodiment 1, and result is identical with embodiment 1.
Claims (1)
1. the preparation method of a spongy ion-exchange fibre, is characterized in that it comprises the steps:
1) the vegetable silk melon and fruit after the normal growth maturation is real, after natural air drying or oven dry, cuts into the long cylinder of 5～15cm, removes the sponge gourd seed of epidermis and hole inside, obtains the cylinder luffa;
2) the cylinder luffa that will get ready carries out pretreatment with one of following two kinds of methods:
A) it is the rectangular-shaped of 0.5cm*0.5cm*0.5cm to 1cm*1cm*1cm that the cylinder luffa that will get ready is cut into the high scope of the wide * of long *, obtains rectangular-shaped luffa; Rectangular-shaped luffa is dipped in distilled water and stirs 1～2h, then luffa is dried 12h in 60～65 ℃ of baking ovens, obtain the dried loofah of fritter;
B) it is highly the small cylinder of 3～7cm that the cylinder luffa that will get ready is sawn into, and obtains the luffa of small cylinder; The luffa of small cylinder is soaked 8～12h in distilled water; Then be placed in 60～65 ℃ of baking ovens and dry 12h, obtain the dried loofah of fritter;
3) activation: the dried loofah of weighing 1～3g fritter, the dried loofah of fritter is placed in the mixed solution of 80～120ml DMF (DMF) and 20-80ml epoxychloropropane, stir 0.5～2h under 70～100 ℃ of condition of water bath heating;
4) catalysis: add 10～40ml pyridine solution to make catalyst, continue 70～100 ℃ of heating water bath 0.5～2h;
5) grafting: add 20～40ml dimethylamine agueous solution, continue 70～100 ℃ of heating water bath 2～4h, obtain the luffa after grafting;
6) clean:
A) luffa after grafting is cooling, the NaOH solution drip washing of use 0.1mol/L 2～3 times, then insert 500ml
,0.1mol/L NaOH solution in, bathe heating and strong stirring 5～10min at 30～40 ℃ of Water Unders;
B) with above-mentioned steps 6) a) resulting luffa 0.1mol/LHCl solution drip washing 2～3 times, then insert 500ml
,0.1mol/LHCl in solution, at 30～40 ℃ of Water Unders, bathe heating and strong stirring 5～10min, regulate pH to neutral;
C) with above-mentioned steps 6) b) resulting luffa is the ethanolic solution drip washing 2～3 times of 50wt% with concentration, then inserts 500ml
,Concentration is in the ethanolic solution of 50wt%, at 30～40 ℃ of Water Unders, bathes heating and strong stirring 5～10min;
D) with above-mentioned steps 6) c) 0.1mol/LNaCl aqueous solution drip washing 2～3 times of resulting luffa, then insert 500ml
,0.1mol/LNaCl in the aqueous solution, at 30～40 ℃ of Water Unders, bathe heating and strong stirring 5～10min, the luffa after being cleaned;
7) luffa after cleaning, in dry 12h under 60～65 ℃ of conditions, obtains spongy ion-exchange fibre;
Described strong stirring refers to that speed of agitator is 200～300r/min.
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| CN104084143A (en) * | 2014-07-23 | 2014-10-08 | 武汉理工大学 | Preparation method of function material in biomass water treatment environment |
| CN104479076B (en) * | 2014-12-05 | 2017-11-14 | 中国科学院长春应用化学研究所 | A kind of hydrophilic luffa |
| CN104939785A (en) * | 2015-07-07 | 2015-09-30 | 马军政 | Towel gourd silk processing process |
| CN109550489A (en) * | 2018-12-03 | 2019-04-02 | 赛恩斯环保股份有限公司 | The preparation method of the ion-exchange fibre of ammonia nitrogen in a kind of absorption waste water |
| CN111346622B (en) * | 2018-12-24 | 2023-05-09 | 内蒙古蒙牛乳业（集团）股份有限公司 | Chromatographic packing and preparation method and application thereof |
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| CN101745367A (en) * | 2008-03-18 | 2010-06-23 | 上海大学 | Application of etherized luffa in metallic ion adsorption as adsorbent |
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