CN1584188A - Preparing method for temperature controlling ionic absorbing fibre - Google Patents
Preparing method for temperature controlling ionic absorbing fibre Download PDFInfo
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- CN1584188A CN1584188A CN 200410025122 CN200410025122A CN1584188A CN 1584188 A CN1584188 A CN 1584188A CN 200410025122 CN200410025122 CN 200410025122 CN 200410025122 A CN200410025122 A CN 200410025122A CN 1584188 A CN1584188 A CN 1584188A
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- irradiation
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Abstract
This invention involves the making method of a kind of temperature-controled adsorption fibre. It belongs to radiate chemistry engineering technology field. The invention mainly uses rediate graft and advance graft. The rediate graft is put the polypropylene fibre in the graft liquid, and then via the transmission equipment put the feedback into the radiate room to radiate.
Description
Technical field
The present invention relates to a kind of temperature control ionic adsorption fiber preparation method, belong to radiation chemistry and technical field of chemical engineering.
Background technology
Processing contains the waste water of metal ion, and method commonly used has electrolysis, the precipitation method, ion-exchange etc.In recent years, the graft modification fiber in the recovery of metal ion, concentrate, enrichment receives much attention with the effect of aspects such as separating.Because graft fibres have advantages such as speed is fast, selectivity is high, easy wash-out regeneration to the absorption of metal ion, value therefore all has a wide range of applications at the aspects such as utilization of metals resources protection, Industrial Wastewater Treatment and marine resources.
Traditional metal ion exchanged resin or fiber generally all utilize strong acid, weak acid root that ion is exchanged, and adopt acid, alkali etc. to carry out technology regeneration such as desorption and washing then, reclaim metal ion simultaneously.No matter traditional ion exchange resin be the wastewater treatment or the enrichment of metal ion, recovery, when obtaining metal ion and water up to standard, can produce a large amount of acid, alkali waste water, also will consume a large amount of pure water.Like this, not only cause the waste of great lot of water resources, also increased the cost of regeneration.Utilize the graft modification fiber to replace ion exchange resin, though the consumption of acid in can corresponding minimizing regenerative process, alkali, but still have waste liquid to produce and the consumption of pure water.
Summary of the invention
The object of the present invention is to provide a kind of graft modification fiber that ionic adsorption or exchange are had temperature sensitivity, utilize high temperature or reduce the purpose that temperature reaches the attached ion of adsorption and desorption.
A kind of temperature control ionic adsorption fiber preparation method of the present invention, the main mutual radiation grafting method that adopts, it is characterized in that, this method has following processing step: polypropylene fibre is immersed in the specific grafting liquid, by transmitting device reaction system is sent into radiation chamber then and carry out irradiation, irradiation bomb adopts gamma-rays, and irradiation dose is 1-50kGy, and the best is 10Kgy; Take out fiber behind the irradiation, the monomer on flush away surface and homopolymers, can obtain the polypropylene fiber with temperature control ionic adsorption-desorption function of graft modification, the prescription of grafting liquid is (percentage by weight): N-N-isopropylacrylamide (NIPAAm) 3-12%, best 5%; Acrylamide (AAm) 1-8%, best 3%; Acrylic acid 0-5%, best 1%; Copper chloride CuCl
20-0.1%, best 0.01%; Surplus is a deionized water; Percent grafting 10-100%, best 25%.
Another temperature control adsorption of metal ions fiber preparation method of the present invention, the main pre-irradiation grafting method that adopts, it is characterized in that, this method has following processing step: polypropylene fibre is sent into radiation chamber by transmitting device carry out irradiation, irradiation bomb adopts gamma-rays, also can use electron beam, irradiation dose is 5-200kGy, and the optimal dose of gamma-ray irradiation is 60Kgy; The optimal dose of electron beam irradiation is 10Kgy; In reactor, inject grafting liquid, feed nitrogen deoxygenation 10 minutes, then the pre-irradiation fiber is immersed in the grafting liquid, logical once more nitrogen deoxygenation 10 minutes, reactor is placed under the suitable hot temperature conditions then and carry out graft reaction, reaction temperature is 20-90 ℃, and the best is 60 ℃; Reaction time is 1-9 hour, and the best is 8 hours; After reaction finishes, take out fiber, the monomer on flush away surface and homopolymers can obtain the polypropylene fiber with temperature control ionic adsorption-desorption function of graft modification, the prescription of grafting liquid is (percentage by weight): N-N-isopropylacrylamide (NIPAAm) 3-12%, best 5%; Acrylamide (AAm) 1-8%, best 3%; Acrylic acid 0-5%, best 1%; Copper chloride CuCl
20-0.1%, best 0.01%; Solvent is a deionized water; Percent grafting 10-100%, best 25%.
The present invention adopts the basic principle of irradiation grafting method as follows:
A. mutual radiation grafting legal system is equipped with temperature control ionic adsorption fiber:
B. the pre-irradiation grafting legal system is equipped with temperature control ionic adsorption fiber:
In the following formula, A is a polypropylene, B is the monomer with temperature sensitivity, as the N-N-isopropylacrylamide etc., adopt the method for radiation, will contain the monomer-grafted of amido, carboxyl and temperature sensitivity in macromolecular fibre, make polymer fiber contain certain functional group, utilize complexing and the hydrophilic-hydrophobic variation of thermosensitive polymer under different temperatures to metal such as acid amides and carboxyl, can be under lower temperature adsorbing metal ions, and under higher temperature desorption.
Fiber behind the employing temperature sensitive hydrogel monomer graft modification, absorption (or exchange) to ion has temperature sensitivity, it is attached to utilize this performance to carry out adsorption and desorption under different temperatures to metal ion, that is to say, can utilize rising (or reduction) temperature to reach the purpose of desorption ion.This has saved acid, neutralizing treatment process not to the utmost, has shortened the required time of regenerating, and has simplified the desorption technology of metal ion, has also significantly reduced the consumption of pure water.In addition, utilize fiber,, the metal ion aqueous solution of high concentration is discharged thereupon, like this, more help concentrating and reclaiming of metal ion the metal ion desorption at a certain temperature by the hydrophobic characteristics of hydrophilic change.
Description of drawings
Fig. 1 is equipped with the schematic flow sheet of temperature control ionic adsorption fiber for mutual radiation grafting legal system of the present invention
Fig. 2 is equipped with the schematic flow sheet of temperature control ionic adsorption fiber for pre-irradiation grafting legal system of the present invention
The specific embodiment
Embodiment one: referring to Fig. 1, present embodiment adopts mutual radiation grafting legal system to be equipped with temperature control ionic adsorption fiber: polypropylene (PP) fiber is immersed in the grafting liquid, by transmitting device reaction system is sent into irradiation Room irradiation then, irradiation bomb adopts gamma-radiation, and dosage is 10kGy.Take out fiber behind the irradiation, the monomer on flush away surface and homopolymers can obtain the PP fiber with temperature control ionic adsorption-desorption function of graft modification.The prescription of grafting liquid is: N-N-isopropylacrylamide (NIPAAm) 5%, and acrylamide (AAm) 3%, acrylic acid are 1%; Copper chloride CuCl
2Be 0.01%, solvent is a deionized water.Percent grafting 25 is advisable.
Embodiment two: referring to Fig. 2, present embodiment adopts pre-irradiation grafting to prepare temperature control ionic adsorption fiber: polypropylene (PP) fiber is introduced radiation field by the irradiation transmitting device carry out irradiation, irradiation bomb adopts gamma-radiation, and dosage is 60kGy.Inject grafting liquid in reactor, letting nitrogen in and deoxidizing immersed the fiber of pre-irradiation in the grafting liquid after 10 minutes, and letting nitrogen in and deoxidizing is 10 minutes once more, then reactor is placed suitable temperature to carry out graft reaction, and reaction temperature is 60 ℃, and the reaction time is 8 hours.After reaction finishes, take out fiber, flush away its surperficial homopolymers and monomer can obtain the PP fiber with temperature control ionic adsorption-desorption function of graft modification.The prescription of grafting liquid is: N-N-isopropylacrylamide (NIPAAm) 5%; Acrylamide (AAm) 3%; Acrylic acid (AAc) 1%; Ferrous sulfate (FeSO
4) 0.01%, solvent is a deionized water.Percent grafting 25%.
The ionic adsorption fiber has been carried out some application tests, and its result is as follows:
1. graft fibres are to the processing of heavy metal ions in wastewater: by test, to heavy metal in the waste water such as Zn
2+, Cd
2+, Hg
2+, Cr
6+, U
6+, Pb
3+, Cu
2+, Fe
2+Deng removal: the percent grafting of selecting fiber for use is 30%; The pH of solution is 1-6, and the best is 1, and temperature is 5-30 ℃, best 20 ℃; The about 0.1-1mmol/g of the adsorption capacity of fiber, maximum 1mmol/g; The concentration of absorption back waste water intermediate ion can be reduced to below the 2-4mg/L.
2. the test of desorption and concentration process: carry out in the aqueous solution of pH=3-10, the best is pH=7; Temperature 40-60 ℃, best 50 ℃.Some concentrate intermediate ion concentration after desorption repeatedly can reach more than the 1000mg/L.Graft fibres after the desorption can use repeatedly.
Percent grafting be 25% o'clock graft fibres under different PH to Fe
2+The adsorption rate of ion (20 ℃, Static Adsorption 5h) sees Table one,
Table one
| ??pH | ????1 | ????3 | ????5 |
| Adsorption rate (%) | ????90 | ????70 | ????45 |
Percent grafting (NIPAAm+AAm) be 25% graft fibres when pH=3 to Fe
2+The desorption of ion concentrates situation (50 ℃, steady-state solution absorption 1h), sees Table 2.
Table 2
| The desorption number of times | ????1 | ????2 | ????3 | ????4 |
| ????Fe 2+Concentration (mg/L) | ????112 | ????221 | ????330 | ????441 |
By last two tables as can be known, Fe
2+The absorption optimum of ion under 20 ℃ of lower temperatures, and at 50 ℃ of following desorption optimums, this is the functional characteristic of temperature control ionic adsorption fiber.
3. graft fibres are to electroplating Fe in (chromium plating, zinc etc.) liquid
2+The selective absorption of ion: the percent grafting of selecting fiber for use is 30%; Under the condition of pH≤1, graft fibres are to Fe
2+The adsorption capacity of ion is greater than Zn
2+Isoionic adsorption capacity, Fe in electroplate liquid
2+The excessive concentration of ion and when influencing electroplating quality, can adopt graft fibres that electroplate liquid is handled makes Fe
2+The concentration of ion drops in the scope of permission.Remove Fe
2+Temperature during ion is 20 ℃.Temperature during desorption is 50 ℃.
Claims (2)
1. temperature control ionic adsorption fiber preparation method, the main mutual radiation grafting method that adopts, it is characterized in that, this method has following processing step: polypropylene fibre is immersed in the specific grafting liquid, by transmitting device reaction system is sent into radiation chamber then and carry out irradiation, radiation source adopts gamma-rays, irradiation dose is 1-50kGy, best for taking out fiber behind the 10Kgy irradiation, the monomer on flush away surface and homopolymers, can obtain the polypropylene fiber with temperature control ionic adsorption-desorption function of graft modification, the prescription of grafting liquid is (percentage by weight): N-N-isopropylacrylamide (NIPAAm) 3-12%, best 5%; Acrylamide (AAm) 1-8%, best 3%; Acrylic acid 0-5%, best 1%; Copper chloride CuCl
20-0.1%, best 0.01%; Solvent is a deionized water; Percent grafting 10-100%, best 25%.
2. temperature control adsorption of metal ions fiber preparation method, the main pre-irradiation grafting method that adopts, it is characterized in that, this method has following processing step: polypropylene fibre is sent into radiation chamber by transmitting device carry out irradiation, radiation source adopts gamma-rays, also can use electron beam, irradiation dose is 5-200kGy, and the optimal dose of gamma-ray irradiation is 60Kgy; The optimal dose of electron beam irradiation is 10Kgy; Inject grafting liquid in reactor, feed the nitrogen deoxygenation, the pre-irradiation fiber is immersed in the grafting liquid again, logical nitrogen deoxygenation 10 minutes places reactor suitable reaching under the hot temperature conditions to carry out graft reaction then, and reaction temperature is 20-90 ℃, and the best is 60 ℃; Reaction time is 1-9 hour, and the best is 8 hours; After reaction finishes, take out fiber, the monomer on flush away surface and homopolymers can obtain the polypropylene fiber with temperature control ionic adsorption-desorption function of graft modification, the prescription of grafting liquid is (percentage by weight): N-N-isopropylacrylamide (NIPAAm) 3-12%, best 5%; Acrylamide (AAm) 1-8%, best 3%; Acrylic acid 0-5%, best 1%; Copper chloride CuCl
20-0.1%, best 0.01%; Solvent is a deionized water; Percent grafting 10-100%, best 25%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410025122 CN1265052C (en) | 2004-06-11 | 2004-06-11 | Preparing method for temperature controlling ionic absorbing fibre |
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|---|---|---|---|
| CN 200410025122 CN1265052C (en) | 2004-06-11 | 2004-06-11 | Preparing method for temperature controlling ionic absorbing fibre |
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| CN1265052C CN1265052C (en) | 2006-07-19 |
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|---|---|---|---|
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101550222B (en) * | 2009-05-11 | 2010-09-29 | 四川省原子能研究院 | A method for preparing radiation graft copolymer of polylactic acid and N-vinyl pyrrolidone |
| CN101967709A (en) * | 2010-04-23 | 2011-02-09 | 临邑县锦源纺织贸易有限公司 | Mixed yarn of intelligent temperature adjustment fibers |
| CN102108112A (en) * | 2011-01-18 | 2011-06-29 | 黑龙江省科学院技术物理研究所 | Pre-irradiation polypropylene graft copolymer and preparation method thereof |
| CN102400375A (en) * | 2010-09-14 | 2012-04-04 | 公安部第一研究所 | Method for producing modified ultrahigh molecular weight polyethylene fiber by using mutual radiation grafting technology |
| CN101632918B (en) * | 2008-07-22 | 2012-07-04 | 天津博纳艾杰尔科技有限公司 | Grafting fiber material with adsorptive action and use method thereof |
| CN104941588A (en) * | 2015-06-01 | 2015-09-30 | 天津工业大学 | Recyclable fiber material capable of quickly removing heavy metal anions |
| CN109208331A (en) * | 2018-08-22 | 2019-01-15 | 安徽利思达网业有限公司 | A kind of monofilament filter cloth hot melt is immobilized-preparation method of co segregation modified dacron filter cloth |
| CN113512225A (en) * | 2021-06-16 | 2021-10-19 | 上海大学 | High critical solution temperature type temperature sensitive hydrogel film and preparation method thereof |
| CN115770626A (en) * | 2022-11-22 | 2023-03-10 | 河南科高辐射化工科技有限公司 | Amphoteric ion exchange fiber and preparation method and application thereof |
-
2004
- 2004-06-11 CN CN 200410025122 patent/CN1265052C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101632918B (en) * | 2008-07-22 | 2012-07-04 | 天津博纳艾杰尔科技有限公司 | Grafting fiber material with adsorptive action and use method thereof |
| CN101550222B (en) * | 2009-05-11 | 2010-09-29 | 四川省原子能研究院 | A method for preparing radiation graft copolymer of polylactic acid and N-vinyl pyrrolidone |
| CN101967709A (en) * | 2010-04-23 | 2011-02-09 | 临邑县锦源纺织贸易有限公司 | Mixed yarn of intelligent temperature adjustment fibers |
| CN102400375A (en) * | 2010-09-14 | 2012-04-04 | 公安部第一研究所 | Method for producing modified ultrahigh molecular weight polyethylene fiber by using mutual radiation grafting technology |
| CN102108112A (en) * | 2011-01-18 | 2011-06-29 | 黑龙江省科学院技术物理研究所 | Pre-irradiation polypropylene graft copolymer and preparation method thereof |
| CN104941588A (en) * | 2015-06-01 | 2015-09-30 | 天津工业大学 | Recyclable fiber material capable of quickly removing heavy metal anions |
| CN109208331A (en) * | 2018-08-22 | 2019-01-15 | 安徽利思达网业有限公司 | A kind of monofilament filter cloth hot melt is immobilized-preparation method of co segregation modified dacron filter cloth |
| CN113512225A (en) * | 2021-06-16 | 2021-10-19 | 上海大学 | High critical solution temperature type temperature sensitive hydrogel film and preparation method thereof |
| CN115770626A (en) * | 2022-11-22 | 2023-03-10 | 河南科高辐射化工科技有限公司 | Amphoteric ion exchange fiber and preparation method and application thereof |
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|---|---|
| CN1265052C (en) | 2006-07-19 |
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