CN102614852A - 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 fibers IEF) is the surface adsorption and the parting material of a fibre-like to ion-exchange fibre, and the exchangeable ion and some same sex ion that mainly lean on the surface active groups of fiber or fibrous polymer to dissociate out exchange; Compare with traditional ion exchange resin, it is big that IEF has specific area, and chemical stability is higher; Mass transfer is apart from weak point, and absorption and desorption rate are fast, adsorptive selectivity strong (metal ion, organic molecule, pernicious gas etc. are had higher adsorptive selectivity); Purify thoroughly; Wash-out and power of regeneration are strong, and energy consumption is low, plurality of advantages such as little and biologically active height of fluid resistance.The isolation of purified of water treatment, gas, the recycling of precious metal ion, the separation and the fields such as extraction and biochemical industry of medicine have been widely used at present; Be to develop new high-tech industry rapidly now; 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 process 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 the ability and the power of regeneration of superpower absorption pernicious gas (sulfur dioxide, ammonia, hydrogen fluoride, hydrogen chloride), has good economy and society benefit.CN 101736525 A have announced a kind of method of the non-weaving cloth by ion-exchange fibre preparation; This non-woven cotton material is applied in the absorbent device of super absorbent polymer; Can improve the water absorbent rate of super absorbent polymer greatly; 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 bar, 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 being used for handling anion-containing waste water.
For the research of ion-exchange fibre, American-European countries, Japan, the former Soviet Union are the research focuses in the west, have had many research report and achievement.The wherein Japanese and former Soviet Union studies early and studies more, the product that for example Japanese TIN and Muscovite VION, FIBAN etc. have formed seriations such as comprising anion, cation, both sexes, chelating.In RU1658444, prepared the fibrous adsorbent that contains carboxyl and diazanyl, ammonia in the gas and ammonium nitrate there are higher purification efficiency.At home; The seventies beginning has been launched the development and the application work of ion exchange fiber material; 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 like CN 1112257C, its product exchange capacity is up to the every gram of 3.0～5.0 mMs, and cost is low, long service life and environmentally safe.
The main technique method of utilizing natural plants raw material or composite fibre materials to prepare ion-exchange fibre is at present further improved with the identical or compound employing of above-mentioned process or on these method bases.The raw material that wherein utilizes natural plants raw material preparing natural plants base ion-exchange fibre is just like agricultural product, agricultural byproducts, agricultural wastes, other plant etc., such as stalk, and rice husk, pericarp, linen-cotton etc.Their key component is a cellulose, also contains hemicellulose, lignin and pectin.
In practical application; The technology simplicity of the ion-exchange fibre of physical arrangement though preparation is kept perfectly; 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 area, temperate zone in Asia; Sponge gourd is one of main vegetables in summer, therefore plants very general in Shanghai, China Jiangsu and Zhejiang Provinces and Guangdong, Guangxi.Generally with tender melon as dish usefulness, 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 are formed; Mainly be made up of cellulose, hemicellulose and lignin, its content of cellulose is up to more than 60%.At present, the research of luffa mainly concentrates on its medical value and preparation shower used in everyday, bath accessory."Compendium of Materia Medica" records Walter context of its organs can, try to wind detoxification, swelling and phlegm, eradicates pain insecticide, governance of various leukemia.Aspect daily use article, existing multinomial invention is like luffa soap, luffa mattress, luffa cleaning brush, luffa shoe-pad or the like.
By on can know, at present all also more original to the processing and the treatment technology of luffa, utilized its natural vascular bundle structure mostly.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of spongy ion-exchange fibre, this method has the advantages that cost is low, absorption property is good.
For realizing above-mentioned purpose, the technical scheme that the present invention taked 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 inner sponge gourd seed of epidermis and hole, obtain cylinder luffa [the string vascular bundle cylinder (strong but pliable in texture) that inside interweaves and is netted];
2) the cylinder luffa of getting ready is carried out preliminary treatment with one of following two kinds of methods:
A) the cylinder luffa of getting ready being cut into the high scope of the wide * of long * is the rectangular-shaped of 0.5cm*0.5cm*0.5cm to 1cm*1cm*1cm, obtains rectangular-shaped luffa (being the luffa fritter); Rectangular-shaped luffa is dipped into stirs 1～2h in the distilled water, then luffa is dried 12h in 60～65 ℃ of baking ovens, obtain the dried loofah of fritter;
B) the cylinder luffa of getting ready being sawn into is the small cylinder of 3～7cm highly, obtains the luffa of small cylinder; The luffa of small cylinder is soaked 8～12h in distilled water; Be placed into then 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 80～120ml N, in the mixed solution of dinethylformamide (DMF) and 20-80ml epoxychloropropane, under 70～100 ℃ of condition of water bath heating, stir 0.5～2h;
4) catalysis: add 10～40ml pyridine solution and make catalyst, continue 70～100 ℃ of water-bath heating 0.5～2h;
5) grafting: add 20～40ml dimethylamine (DMA) (concentration is 33wt%) aqueous solution, continues 70～100 ℃ of water-baths and heat 2～4h, obtain the luffa (preliminary product) after the grafting;
6) clean:
A),, insert 500ml again with the NaOH solution drip washing of 0.1mol/L 2～3 times with the luffa after grafting cooling (being cooled to below 20 ℃)
,0.1mol/L NaOH solution in, water-bath heating and the powerful 5～10min of stirring (removing ash content, residue, part polysaccharide material) under 30～40 ℃ of conditions;
B) with above-mentioned steps 6) a) resulting luffa insert 500ml again with 0.1mol/LHCl solution drip washing 2～3 times
,0.1mol/LHCl in the solution, water-bath heating and the powerful 5～10min that stirs regulate pH to neutral under 30～40 ℃ of conditions;
C) with above-mentioned steps 6) b) resulting luffa uses concentration as the ethanolic solution drip washing of 50wt% 2～3 times, inserts 500ml again
,Concentration is in the ethanolic solution of 50wt%, water-bath heating and the powerful 5～10min (removing residual organic reactant) that stirs under 30～40 ℃ of conditions;
D) with above-mentioned steps 6) c) resulting luffa is with 0.1mol/LNaCl aqueous solution drip washing 2～3 times, inserts 500ml again
,0.1mol/LNaCl in the aqueous solution, water-bath heating and the powerful 5～10min that stirs under 30～40 ℃ of conditions, the luffa after obtaining cleaning;
7) luffa after will cleaning obtains spongy ion-exchange fibre (final products, sealing is stored in drier, and is subsequent use) under 60～65 ℃ of conditions, drying 12h.
Said powerful the stirring is meant that speed of agitator is 200～300r/min.
Utilizing water-bath to heat mode that electronic stirring or water-bath heating and magnetic agitation carry out simultaneously cleans product and takes off slag.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 come the development and preparation ion-exchange fibre for raw material; Prepare raw material and compared with techniques with existing ion-exchange fibre; The characteristics that possess cost low (economy), facility and environmental protection (cleaning) all are significant for the means, approach and the novelty that improve China's ion-exchange fibre preparation.
The invention has the beneficial effects as follows: the product sponge gourd ripening fruits with crops is a feedstock production natural plants ion-exchange fibre, has opened up kind and preparation approach that the natural plants ion-exchange fibre prepares raw material, compares with the preparation approach of existing ion-exchange fibre; Preparation technology is simple and clear, weak point consuming time, 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 a process chart of the present invention.
Fig. 2 is that the embodiment of the invention 1 obtains the absorption figure of spongy ion-exchange fibre to nitrate ion.
Fig. 3 is that the embodiment of the invention 1 obtains spongy ion-exchange fibre regeneration tests curve map.
The specific embodiment
In order to understand the present invention better, further describe content of the present invention below in conjunction with specific embodiment, but content of the present invention not only is confined to following embodiment.
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 inner sponge gourd seed of epidermis and hole, obtain cylinder luffa [the string vascular bundle cylinder (strong but pliable in texture) that inside interweaves and is netted];
2) the cylinder luffa of getting ready is carried out preliminary treatment: the structure that the cylindrical shape luffa of getting ready is cut into a large amount of similar little cuboids with clean scissors; 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); Put into the beaker of the 10L that cleaned with distilled water to the rectangular-shaped luffa that shears, pour distilled water 6～8L into, soak, stir with electric mixer simultaneously, the luffa fritter is fully mixed with distilled water contact; Immersion is also stirred 1～2h, then the luffa fritter is poured in the clean screen cloth, and related screen cloth is put into baking oven at 60～65 ℃ of oven dry 12h, obtains the dried loofah of fritter;
3) activation: from baking oven, take out above dried loofah, the dried loofah of weighing 1g fritter is put into the flask with three necks,round bottom of 1L; Two side mouths of there-necked flask cover with glass cover and (annotate: uncap when needs add medicine only; Add the medicine continued and cover, all so operations in the entire reaction course), 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 is opened electronic stirring and is continued to mix solution and (make the abundant haptoreaction of luffa and reagent; Rotating speed is at 60～100r/min, and stirring does not stop in the entire reaction course) water-bath heating 0.5～1h under 85 ℃ of conditions;
4) catalysis: add the 10ml pyridine solution and make catalyst, water-bath heating 1h under 100 ℃ of conditions;
5) grafting: add 30ml dimethylamine (DMA) (concentration the is 33wt%) aqueous solution, continues 100 ℃ of water-baths and heat 3h, obtain the luffa (preliminary product) after the grafting;
6) clean:
A) cooling of the luffa after the grafting (is poured out preliminary product to clean screen cloth from there-necked flask; Be cooled to below 20 ℃; Transfer in the 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, pour 500ml into
,0.1mol/L NaOH solution in, water-bath heating and the powerful 5～10min of stirring under 30 ℃ of conditions (remove ash content, residue, part polysaccharide material, said powerful the stirring is meant that speed of agitator is 200～300r/min, below identical);
B) with above-mentioned steps 6) a) resulting luffa then luffa is transferred in the 500ml large beaker with 0.1mol/LHCl solution drip washing 2～3 times, pour 500ml into
,0.1mol/LHCl in the solution, water-bath heating and the powerful 5～10min that stirs regulate pH to neutral under 30 ℃ of conditions;
C) with above-mentioned steps 6) b) resulting luffa uses concentration as the ethanolic solution drip washing of 50wt% 2～3 times, then luffa is transferred in the 500ml large beaker, pours 500ml into
,Concentration is in the ethanolic solution of 50wt%, water-bath heating and the powerful 5～10min (removing residual organic reactant) that stirs under 30～40 ℃ of conditions;
D) with above-mentioned steps 6) c) resulting luffa is with 0.1mol/LNaCl aqueous solution drip washing 2～3 times, then luffa is transferred in the 500ml large beaker, pours 500ml into
,0.1mol/LNaCl in the aqueous solution, water-bath heating and powerful 5～10min, the luffa after obtaining (purpose is thorough wash off product) of stirring under 30～40 ℃ of conditions;
7) luffa after will cleaning goes to screen cloth, under 60～65 ℃ of conditions, dries 12h, obtains spongy ion-exchange fibre (final products, sealing is stored in drier, and is subsequent use).
For performance and the effect that shows this spongy ion-exchange fibre better, nitrate ion in the water is inhaled with it
Attach the test of performance, concrete experimental technique is following:
Take by weighing many parts of 0.1g embodiment 1 products obtained therefroms, put into the iodine flask of clean 250ml respectively, pour 50ml 50mg/L into
The KNO of (referring to nitrate concentration)
3The aqueous solution is built lid, and in temperature (20 ± 1 ℃) vibration down, oscillation intensity is 120r/min, vibration 60min.Nitrate ion concentration is measured with the nitrate anion assay method shown in the GBT 8538-1995, related experiment result such as table 1 (scheming as shown in Figure 2).
Can get behind the product contact solution by absorption-time graph and to be adsorbed as quick absorption in 30 minutes; 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.
Table 1 product dosage is to the influence of 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 inner sponge gourd seed of epidermis and hole, obtain cylinder luffa [the string vascular bundle cylinder (strong but pliable in texture) that inside interweaves and is netted];
2) the cylinder luffa of getting ready is carried out preliminary treatment: the structure that the cylindrical shape luffa of getting ready is cut into a large amount of similar little cuboids with clean scissors; The scope that the wide * of long * is high is 0.5cm*0.5cm*0.5cm to 1cm*1cm*1cm; Put into the beaker of the 10L that cleaned with distilled water to the fritter that shears, pour distilled water 6～8L into, soak; Stir with electric mixer simultaneously, the luffa fritter is fully mixed with distilled water contact; Immersion is also stirred 1～2h, then the luffa fritter is poured in the clean screen cloth, and 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 with glass cover that (annotate: uncap when needs add medicine only adds the medicine continued and covers; All so operations in the entire reaction course); Stretch into electric mixer from there-necked flask master mouth, add 120ml N, dinethylformamide (DMF) solution with little glass funnel from there-necked flask side mouth; 80ml epoxychloropropane solution; Open electronic stirring and continue to mix solution (make the abundant haptoreaction of luffa and reagent, rotating speed is at 60～100r/min, stirs in the entire reaction course not stop) water-bath heating 1h under 100 ℃ of conditions;
4) catalysis: add the 10ml pyridine solution and make catalyst, water-bath heating 1h under 100 ℃ of conditions;
5) grafting: add dimethylamine (DMA) aqueous solution of 30ml 33 wt %, water-bath heating 3h under 100 ℃ of conditions obtains the luffa (preliminary product) after the grafting;
6) clean:
A) luffa after the grafting (preliminary product) is poured out from there-necked flask to clean screen cloth, be cooled to below 20 ℃, transfer in the 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 water-bath heating are also decoloured and are got rid of and take off residue in the hole with powerful stirring of electric mixer; 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 insert 500ml again with 0.1mol/LHCl solution drip washing 2～3 times
,0.1mol/LHCl in the solution, (speed of agitator is 200～300r/min), regulates pH to neutral for water-bath heating and powerful stirring 5～10min under 30～40 ℃ of conditions;
C) with above-mentioned steps 6) b) resulting luffa uses concentration as the ethanolic solution drip washing of 50wt% 2～3 times, inserts 500ml again
,Concentration is in the ethanolic solution of 50wt%, water-bath heating and the powerful 5～10min (speed of agitator is 200～300r/min, removes residual organic reactant) that stirs under 30～40 ℃ of conditions;
D) with above-mentioned steps 6) c) resulting luffa is with 0.1mol/LNaCl aqueous solution drip washing 2～3 times, inserts 500ml again
,0.1mol/LNaCl in the aqueous solution, (speed of agitator is 200～300r/min), the luffa product after obtaining cleaning for water-bath heating and powerful stirring 5～10min under 30～40 ℃ of conditions;
7) the luffa product after will cleaning goes to screen cloth, under 60～65 ℃ of conditions, dries 12h, obtains spongy ion-exchange fibre (final products, sealing is stored in drying box, and is subsequent use).
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 inner sponge gourd seed of epidermis and hole, obtain cylinder luffa [the string vascular bundle cylinder (strong but pliable in texture) that inside interweaves and is netted];
2) the cylinder luffa of getting ready is carried out preliminary treatment: the structure that the cylindrical shape luffa of getting ready is cut into a large amount of similar little cuboids with clean scissors; The scope that the wide * of long * is high is 0.5cm*0.5cm*0.5cm to 1cm*1cm*1cm; Put into the beaker of the 10L that cleaned with distilled water to the fritter that shears, pour distilled water 6～8L into, soak; Stir with electric mixer simultaneously, the luffa fritter is fully mixed with distilled water contact.Immersion is also stirred 1～2h, then the luffa fritter is poured in the clean screen cloth, and related screen cloth is put into baking oven at 60～65 ℃ of oven dry 12h, obtains the dried loofah of fritter;
3) activation: raw material (dried loofah of fritter) in more than from baking oven, taking out; 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 with glass cover that (annotate: uncap when needs add medicine only adds the medicine continued and covers; All so operations in the entire reaction course), 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; Open electronic stirring and continue to mix solution (make the abundant haptoreaction of luffa and reagent, rotating speed is at 60～100r/min, stirs in the entire reaction course not stop) water-bath heating 1h under 100 ℃ of conditions;
4) catalysis: add the 20ml pyridine solution and make catalyst, water-bath heating 1h under 100 ℃ of conditions;
5) grafting: add dimethylamine (DMA) aqueous solution of 40ml (concentration is 33wt%), water-bath heating 3h under 100 ℃ of conditions obtains the luffa (preliminary product) after the grafting;
6) clean: a) preliminary product is poured out from there-necked flask to clean screen cloth, be cooled to below 20 ℃, transfer in the 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, the water-bath heating is also decoloured with the powerful stirring of electric mixer and is got rid of and take off residue in the hole for 30 ℃; 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 insert 500ml again with 0.1mol/LHCl solution drip washing 2～3 times
,0.1mol/LHCl in the solution, (agitator is used magnetic stirring apparatus, and agitator speed 200～300r/min) is regulated pH to neutral for water-bath heating and powerful stirring 5～10min under 30～40 ℃ of conditions;
C) with above-mentioned steps 6) b) resulting luffa uses concentration as the ethanolic solution drip washing of 50wt% 2～3 times, inserts 500ml again
,Concentration is in the ethanolic solution of 50wt%, water-bath heating and the powerful 5～10min (agitator speed 200～300r/min removes residual organic reactant) that stirs under 30～40 ℃ of conditions;
D) with above-mentioned steps 6) c) resulting luffa is with 0.1mol/LNaCl aqueous solution drip washing 2～3 times, inserts 500ml again
,0.1mol/LNaCl in the aqueous solution, water-bath heating and powerful 5～10min, the luffa after obtaining of stirring under 30～40 ℃ of conditions;
7) luffa after will cleaning changes sand core funnel over to, and the luffa after cleaning under 60～65 ℃ of conditions, drying 12h, is obtained spongy ion-exchange fibre (final products, sealing is stored in drying box, and is subsequent use).
The experimental technique experiment condition of embodiment 3 eliminating rate of absorption is with embodiment 1, and the 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 is regenerated-adsorption experiment, experimental technique and result are following:
Get the saturated product of absorption of the 0.1g of equivalent,, be transferred to the common centrifuge tube of 50ml with a small amount of 0.1mol/LNaCl solution drip washing 2～3 times; Add the NaOH solution of the 0.1mol/L of 30ml, behind the centrifugal 30min, the drip washing of 0.1mol/LNaCl solution is 2～3 times again in centrifuge; Washed with de-ionized water 2 times; Dry 12h down at 60 ℃, adsorb and desorption experiment gained result such as Fig. 3 again.
Experiment condition: the KNO of 50ml 50mg/L (referring to nitrate concentration)
3The aqueous solution; Spongy exchange fiber dosage 0.1g;
20 ± 1 ℃ of temperature; Vibration rotating speed 120r/min; Duration of oscillation 60min.
Can know that by the exchange regeneration tests product is long life cycle, adsorption capacity reduces slower, does not have tangible downward trend, and only testing to ten secondaries, the 0.1g reconstituted product still can keep 77.5% clearance to the nitrate ion of experimental solutions.
Embodiment 4: basic identical with embodiment 2, difference is that the bath temperature of three reactions step is followed successively by: 85 ℃, 100 ℃, 85 ℃.
The experimental technique experiment condition of eliminating rate of absorption is with embodiment 2, and the result is identical with embodiment 2.
Regeneration tests is with embodiment 1, and the result is identical with embodiment 1.
Embodiment 5: basic identical with embodiment 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 the result is identical with embodiment 2.
Regeneration tests is with embodiment 1, and the result is identical with embodiment 1.
Embodiment 6: basic identical with embodiment 2, what difference was that raw material uses is complete small cylinder shape luffa. the reaction drug dosage multiply by (small cylinder shape luffa quality/2g).There-necked flask replaces with the bigbore beaker of 1L, but uses the magnetic stirring apparatus heated and stirred of temperature control.
The experimental technique experiment condition of eliminating rate of absorption is with embodiment 2, and the result is identical with embodiment 2.
Regeneration tests is with embodiment 1, and the result is identical with embodiment 1.
Embodiment 7: basic identical with embodiment 2, difference is: 2) the cylinder luffa of getting ready is carried out preliminary treatment: it is the small cylinder of 3～7cm highly that the cylinder luffa of getting ready is sawn into, and obtains the luffa of small cylinder; The luffa of small cylinder is soaked 8～12h in distilled water; Be placed into then 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 the result is identical with embodiment 2.
Regeneration tests is with embodiment 1, and the result is identical with embodiment 1.
Embodiment 8: basic identical with embodiment 2, difference is: catalysis: add the 40ml pyridine solution and make catalyst, continue 70 ℃ of water-bath heating 0.5.
The experimental technique experiment condition of eliminating rate of absorption is with embodiment 2, and the result is identical with embodiment 2.
Regeneration tests is with embodiment 1, and the result is identical with embodiment 1.
Embodiment 9: basic identical with embodiment 2, difference is: catalysis: add the 40ml pyridine solution and make catalyst, continue 70 ℃ of water-bath heating 2h.
The experimental technique experiment condition of eliminating rate of absorption is with embodiment 2, and the result is identical with embodiment 2.
Regeneration tests is with embodiment 1, and the result is identical with embodiment 1.
Embodiment 10: basic identical with embodiment 2, difference is: grafting: add 20ml dimethylamine (DMA) (concentration the is 33wt%) aqueous solution, continues 70 ℃ of water-baths and heat 2h, obtain the luffa (preliminary product) after the grafting.
The experimental technique experiment condition of eliminating rate of absorption is with embodiment 2, and the result is identical with embodiment 2.
Regeneration tests is with embodiment 1, and the result is identical with embodiment 1.
Embodiment 11: basic identical with embodiment 2, difference is: grafting: add 20ml dimethylamine (DMA) (concentration the is 33wt%) aqueous solution, continues 70 ℃ of water-baths and heat 4h, obtain the luffa (preliminary product) after the grafting.
The experimental technique experiment condition of eliminating rate of absorption is with embodiment 2, and the result is identical with embodiment 2.
Regeneration tests is with embodiment 1, and the result is identical with embodiment 1.
Claims (2)
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 inner sponge gourd seed of epidermis and hole, obtains the cylinder luffa;
2) the cylinder luffa of getting ready is carried out preliminary treatment with one of following two kinds of methods:
A) the cylinder luffa of getting ready being cut into the high scope of the wide * of long * is the rectangular-shaped of 0.5cm*0.5cm*0.5cm to 1cm*1cm*1cm, obtains rectangular-shaped luffa; Rectangular-shaped luffa is dipped into stirs 1～2h in the distilled water, then luffa is dried 12h in 60～65 ℃ of baking ovens, obtain the dried loofah of fritter;
B) the cylinder luffa of getting ready being sawn into is the small cylinder of 3～7cm highly, obtains the luffa of small cylinder; The luffa of small cylinder is soaked 8～12h in distilled water; Be placed into then 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 80～120ml N, in the mixed solution of dinethylformamide (DMF) and 20-80ml epoxychloropropane, under 70～100 ℃ of condition of water bath heating, stir 0.5～2h;
4) catalysis: add 10～40ml pyridine solution and make catalyst, continue 70～100 ℃ of water-bath heating 0.5～2h;
5) grafting: add 20～40ml dimethylamine agueous solution, continues 70～100 ℃ of water-baths and heat 2～4h, obtain the luffa after the grafting;
6) clean:
A),, insert 500ml again with the NaOH solution drip washing of 0.1mol/L 2～3 times with the luffa after grafting cooling
,0.1mol/L NaOH solution in, water-bath heating and the powerful 5～10min that stirs under 30～40 ℃ of conditions;
B) with above-mentioned steps 6) a) resulting luffa insert 500ml again with 0.1mol/LHCl solution drip washing 2～3 times
,0.1mol/LHCl in the solution, water-bath heating and the powerful 5～10min that stirs regulate pH to neutral under 30～40 ℃ of conditions;
C) with above-mentioned steps 6) b) resulting luffa uses concentration as the ethanolic solution drip washing of 50wt% 2～3 times, inserts 500ml again
,Concentration is in the ethanolic solution of 50wt%, water-bath heating and the powerful 5～10min that stirs under 30～40 ℃ of conditions;
D) with above-mentioned steps 6) c) resulting luffa is with 0.1mol/LNaCl aqueous solution drip washing 2～3 times, inserts 500ml again
,0.1mol/LNaCl in the aqueous solution, water-bath heating and the powerful 5～10min that stirs under 30～40 ℃ of conditions, the luffa after obtaining cleaning;
7) luffa after will cleaning obtains spongy ion-exchange fibre under 60～65 ℃ of conditions, drying 12h.
2. a kind of method of utilizing agricultural product to prepare the natural plants ion-exchange fibre according to claim 1 is characterized in that: said powerful the stirring is meant that speed of agitator is 200～300r/min.
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| 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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