CN1363426A - Ion exchange fibre and its synthesizing process - Google Patents

Abstract

An alkaline ion-exchanging fibre adsorbent with adsorption to F, PO4 and SO4 ions in water is a trimer containing amido radicals (14-22 wt.%) of acrylonitrile, perspex and itaconate. Its preparing process is also disclosed. Its advantages include high adsorption capacity and speed, high mechanical and chemical stabilities, and long storage period (more than 3 years).

Description

A kind of ion-exchange fibre and synthetic method thereof

The present invention relates to a kind of ion-exchange fibre and synthetic method thereof, specifically, the present invention relates to a kind ofly can remove anion F in the water ^-, PO ₄ ^3-, SO ₄ ^2-Ion-exchange fibre and preparation method thereof.

Along with social economy constantly develops, China's water resource is in short supply day by day and the water pollution situation constantly increases the weight of, and about 60% underground water is subjected to F ^-, PO ₄ ^3-, SO ₄ ^2-, AsO ₄ ^3-Pollution Deng harmful anion, add up according to investigations, the whole nation has 7,700 ten thousand populations to quote high-fluorine water approximately, pollutant levels are low because the water yield is big, conventional water treatment process is difficult to effectively remove these micropollutants, makes supply and demand water contradiction become increasingly conspicuous, and this has not only seriously restricted China's sustainable economic development, and directly endangering people's health, influence social stability.Adsorption filtration is the significant element technology during current profound purification is handled, and no matter in the city water purified treatment, municipal sewage and industrial wastewater circular regeneration all have extremely extensive use in handling.At present, sorbing material commonly used has active carbon, activated alumina and ion exchange resin etc., though they can adsorb all contaminations effectively, because its lower adsorption capacity, slower adsorption rate and relatively poor mechanical stability etc. are restricted its extensive use.Therefore, research and develop the sorbing material of new and effective economy, utilize difficulty for solving the large-scale resource regeneration of China, the little pollution problem of underground water has crucial society and economic implications undoubtedly.

As a kind of new and effective economic absorption filtering material, must possess three primary conditions: 1) efficient, promptly have efficient absorption usefulness, applied widely; 2) stable, promptly novel absorption material should have stable chemical properties, can the long period operation, and iterative regenerable and not losing efficacy; 3) economy, commercially available relative low price, it is low especially to move the regeneration expense.Only satisfying under these three primary condition situations, this novel absorption filtering material just has actual application prospect.

The ion-exchange fibre sorbing material adopt by economic synthetic fibers as: polyvinyl chloride, polyvinyl alcohol and polyacrylonitrile fibre etc. are raw material, through chemical modification, graft copolymerization etc. are handled step by step, make it on fiber reinforcement to introduce the various active functional group and make the fibrous material with yin, yang ion-exchange group or chelate functional base.The ion-exchange fibre sorbing material combines the advantage separately of granular ion exchange resin and fiber filter material, and therefore, it is at chemical analysis, chemical separating, and industry such as cleaner production and resource recycling, environmental protection have broad application prospects in the field.

This research at present is in Europe, the United States, moral, day, and all to become focus, large-scale production is studied at most and formed to existing many research report and patent achievements wherein with the Japan and the former Soviet Union in states such as the former Soviet Union.SU1658444 has synthesized the fibrous adsorbent that contains carboxyl and diazanyl, is used for the purified treatment of gas ammonia and ammonium nitrate.It is raw material that RU1051989 has introduced with the polyacrylonitrile fibre, and in succession with hydrazine hydrate or hydrazine sulfate, the sodium hydroxide solution reaction is handled with hydrazine hydrate again, makes the synthetic method of modified polyacrylonitrile chelate fibre.RU2044748 carries out cross-linking reaction with polyacrylonitrile fibre and hydrazine hydrate, and then reacts with sodium hydroxide solution, has synthesized the cation exchange fibre adsorbent.In SU1512984, successively, prepared the ion-exchange chelate fibre that contains amino, hydroxyl oximido with polyacrylonitrile fibre and azanol, polyethylene polyamine reaction.CN1172870A and ZL97120341.5 are that skeleton has prepared respectively and contains carboxyl, hydrazide group, amino and phosphonate group and imidazolinyl chelate fibre with the polyacrylonitrile fibre.In sum, at present these fiber adsorbing substances of development are mainly used in the absorption and the removal of metal cation such as heavy metal ion, precious metal ion, but still belong to blank at home and abroad to the ion-exchange fibre that harmful anion in the water has an absorption property.

The objective of the invention is to seek that synthesis technique is simple, preparation cost is cheap, the ion-exchange fibre sorbing material of good mechanical stability, good adsorption performance and preparation method thereof, make it be used for water anion F ^-, PO ₄ ^3-, SO ₄ ^2-Absorption and removal.

The invention provides a kind of to F in the water ^-, PO ₄ ^3-, SO ₄ ^2-Ion has the alkalinous ion-exchange fibre absorbent of absorption property, and this alkalinous ion-exchange fibre absorbent is the acrylonitrile-methyl methacrylate-itaconic ester trimer of amino-contained functional group, and wherein the content of amido is 14-22% (weight).

The present invention also provides a kind of method for preparing alkalinous ion-exchange fibre absorbent of the present invention, comprising:

With acrylonitrile-methyl methacrylate-itaconic ester trimer under 90～98 ℃, with percent by volume be 20～40% hydrazine hydrochloride reaction 3～5 hours;

Then under 90～95 ℃, with concentration of volume percent be 30～45% reacting ethylenediamine 8～12 hours, be 30～45% diethylenetriamine reaction 13～17 hours perhaps with concentration of volume percent;

Is that 40～50 ℃, concentration are to soak 1～2 hour in the hydrochloric acid solution of 1～2mol/L with the product of gained in temperature.

The prepared fiber adsorbing substance of the present invention has the following advantages:

1) fibrous raw material is cheap and easy to get, and synthesis step is simple, and process equipment is few, easy operating.

2) this product is to F in the water ^-, PO ₄ ^3-, SO ₄ ^2-The adsorption capacity of ion is big, and adsorption rate is fast,

In 5 minutes, can reach adsorption equilibrium.

3) product machinery and chemical stability are good, and long preservation is more than 3 years, and absorption property keeps not

Become.

Embodiment 1:

Take by weighing acrylonitrile-methyl methacrylate-itaconic ester trimer fiber 20g in the 1.25L reactor, add the 1000mL percent by volume and be 20～40% hydrazine hydrochloride, in oil bath, be heated to 90～98 ℃, and under this temperature constant temperature 3～5 hours.Take out back cooling naturally,, dry down with big water gaging flushing at 60～80 ℃ to neutral.

Above-mentioned dry products put into fill that the 1000mL concentration of volume percent is 30～45%, temperature is the reactor of 60 ℃ ethylenediamine, reacted after 8～12 hours heat temperature raising to 90～95 ℃, take out cold slightly, with big water gaging flushing to neutral.

Then, it is in 40～50 ℃ the hydrochloric acid solution that the said goods is immersed in 1～2mol/L, temperature, keeps after 1～2 hour, takes out fiber, with a large amount of hot washes to neutrality.50～60 ℃ of following dried overnight, promptly get final products.

Embodiment 2:

Take by weighing acrylonitrile-methyl methacrylate-itaconic ester trimer fiber 20g in the 1.25L reactor, add the 1000mL percent by volume and be 20～40% hydrazine hydrochloride, in oil bath, be heated to 90～98 ℃, and under this temperature constant temperature 3～5 hours.Take out back cooling naturally,, dry down with big water gaging flushing at 60～80 ℃ to neutral.

Above-mentioned dry products put into fill that the 1000mL concentration of volume percent is 30～45%, temperature is the reactor of 60 ℃ diethylenetriamine, reacted after 13～17 hours heat temperature raising to 90～95 ℃, take out cold slightly, with big water gaging flushing to neutral.

Then, it is in 40～50 ℃ the hydrochloric acid solution that the said goods is immersed in 1～2mol/L, temperature, keeps after 1～2 hour, takes out fiber, with a large amount of hot washes to neutrality.50～60 ℃ of following dried overnight, promptly get final products.

The weight percent content of N and O element is respectively 14-20% and 13-14% in the product of the present invention.The content of amido is 14-22% (weight).

Adopt the Staticadsorption experiment technology to the prepared ion-exchange fibre adsorbent of embodiment 1 to F ^-, PO ₄ ^3-, SO ₄ ^2-The absorption property of ion is studied, and concrete grammar is as follows: take by weighing the 0.1g fiber adsorbing substance in the ground Erlenmeyer flask, add 25mL and contain F ^-5mg/L, PO ₄ ^3-20mg/L, SO ₄ ^2-The mixing test solution of 15mg/L, to certain pH value, 25 ℃ of following constant temperature vibrations 24 hours, suction filtration was with each ion concentration of residue in the ion-chromatographic determination filtrate, according to initial and residual F with rare NaOH and HCl solution regulation system ^-, PO ₄ ^3-, SO ₄ ^2-Ion concentration is calculated its absorption percentage, the results are shown in Table 1.

Table 1 ion-exchange fibre is to F ^-, PO ₄ ^3-, SO ₄ ^2-The absorption percentage (%) of ion

Former water pH

Ion 2.79 3.50 4.53 5.68 7.01

F ^- 58.38 79.49 82.81 86.00 81.30

PO ₄ ^3- 88.50 96.88 98.13 97.58 96.00

SO ₄ ^2-47.70 the concentration of each ion is respectively in the 92.13 97.29 95.26 94.20 former water: F ^-5mg/L, PO ₄ ^3-20mg/L, SO ₄ ^2-15mg/L, fiber consumption: 0.1g/25mL

Utilize the prepared ion-exchange fibre adsorbent of embodiment 2 to F ^-Ion remaval dynamics is studied, and concrete grammar is as follows: take by weighing the 0.5g fiber adsorbing substance in the beaker of 1L, add 500mL and contain 2,5 and the F of 10mg/L ^-The ion test solution at room temperature stirs, timing at once, and in the different time sampling, suction filtration is with residual F in the ion-chromatographic determination filtrate ^-Ion concentration is calculated fiber adsorbing substance and is removed F ^-The ion percentage the results are shown in Table 2.

Table 2 under different times of contact ion-exchange fibre to F ^-Removal percentage (%) F ion concentration time of contact (min) of ion is 25 10 30 60 2 97.70 98.30 98.30 98.30 98.30 5 89.20 94.70 95.20 95.40 95.0010 84.72 92.41 92.78 92.78 92.87 fiber adsorbing substance consumption: 1g/L (mg/L), former water volume: 500mL, former water pH value: 5-6.

Claims (2)

1. ion-exchange fibre adsorbent, acrylonitrile-methyl methacrylate that this ion-exchange fibre adsorbent is the amino-contained functional group-itaconic ester trimer, wherein the content of amido is 14-22% (weight).

2. method for preparing the described ion-exchange fibre adsorbent of claim 1 comprises:

With acrylonitrile-methyl methacrylate-itaconic ester trimer under 90～98 ℃, with percent by volume be 20～40% hydrazine hydrochloride reaction 3～5 hours;

Then under 90～95 ℃, with concentration of volume percent be 30～45% reacting ethylenediamine 8～12 hours, be 30～45% diethylenetriamine reaction 13～17 hours perhaps with concentration of volume percent;

Is that 40～50 ℃, concentration are to soak 1～2 hour in the hydrochloric acid solution of 1～2mol/L with the product of gained in temperature.