CN104941588A - Recyclable fiber material capable of quickly removing heavy metal anions - Google Patents
Recyclable fiber material capable of quickly removing heavy metal anions Download PDFInfo
- Publication number
- CN104941588A CN104941588A CN201510311532.1A CN201510311532A CN104941588A CN 104941588 A CN104941588 A CN 104941588A CN 201510311532 A CN201510311532 A CN 201510311532A CN 104941588 A CN104941588 A CN 104941588A
- Authority
- CN
- China
- Prior art keywords
- bromo
- fibrous material
- heavy metal
- fiber
- metal anion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention relates to a recyclable fiber material capable of quickly removing heavy metal anions. A fiber base material is placed into a monomer solution containing double bonds and tertiary amino groups, and is irradiated to obtain tertiary amino group grafted functional fiber; then the prepared functional fiber is subjected to quaternization reaction by selection of brominated alkanes, so as to obtain the brominated quaternized functional fiber. The obtained brominated quaternized functional fiber can remove 80-99% of the heavy metal anions in the solution within 2-30 min, and the desorbed fiber can be repeatedly used for more than 20 times. The preparation process is simple, the condition is mild, and use of a strong carcinogen is avoided; moreover, the prepared functional fiber has the advantages that the adsorption speed is quick, the adsorption agent consumption is less, the removal rate is high, and the separation and regeneration are easy. The recyclable fiber material can be used for efficiently removing the heavy metals existing in the anion form in wastewater.
Description
Technical field
The invention belongs to functional material and field of environment engineering, particularly a kind of fibrous material of the quick removal heavy metal anion that can be recycled.
Background technology
Along with developing rapidly of modern industry, many pollutants containing heavy metal ion enter air, water and soil environment, cause serious environmental pollution.Heavy metal ion is not easily decomposed, and easily causes secondary pollution, can be accumulated by the bioconcentration of food chain, just can endanger healthy once take in human body.In numerous heavy metal, one of typical environment persistent pollutant that chromium and Shen Shi UNEP (United Nations Environment Program) announce, it exists mainly with anionic state in aqueous, Cr (VI) has good water-soluble, strong oxidizing property, toxicity is 100 times of Cr (III), drink pollution of chromium water for a long time, easily bring out the organ lesions such as bladder, kidney, liver, even likely cause skin canceration [W.B.Zhang, et al.Ultrasound-Enhanced Adsorption of Chromium (VI) on Fe
3o
4magnetic Particles [J] .Industrial & Engineering Chemistry Research, 2014,53 (1): 333-339].Therefore, remove and reduce the concentration of heavy metal anion in water and become most important.
In current water, the processing method of heavy metal mainly contains chemical reduction method, chemical precipitation method, ion-exchange, hyperfiltration, membrane separation process, electrocoagulation, absorption method etc.Wherein absorption method due to have simple to operate, small investment, efficiency are high, be easy to the advantages such as recovery be widely used in process industrial wastewater [Hu Haixiang. heavy metal wastewater thereby Treatment process overview and developing direction [J]. Chinese Resources fully utilize, 2008,26 (2): 22-25].A lot of material containing tertiary amine groups and quaternary ammonium group has been used to the Cr (VI) in adsorbent solution, as [the J.Huang such as polymer absorbant of resin, active carbon, biomaterial, nanotube, gel, shitosan, synthesis, et al.Polyphenylene sulfide based anion exchange fiber:Synthesis, characterization and adsorption of Cr (VI), Journal of Environmental Sciences 2012,24 (16) 1433-1438].But the character of some materials limits the application of itself, as the impurity in adsorbent, lower adsorption rate and desorption rate, production cost is high, recycles difficulty large, even causes the problems such as second time pollution.
Fibrous adsorbent is a kind of novel adsorption and separation material, has more effective specific area, absorption and resolution speed soon, higher desorption efficiency and regenerability.Alkaline functional fiber used at present adopts first chloromethylation mostly, and then carries out ammonium and obtain quaternary ammoniated strong basicity functional fibre.But the chloromethyl ether with strong carcinogenicity or dichlormethyl ether to be used in chloromethylation process, also make with the additive-crosslinking of methylene exchange capacity reduce in chloromethylation simultaneously.
At present, for avoiding the use of strong carcinogen, Lv Xianghua adopts polyacrylonitrile (PAN) to be matrix fiber, first with triethylene tetramine Reactive Synthesis polyamines base ion-exchange fibre, synthesize quaternary ammonium group ion-exchange fibre again [Lv Xianghua, containing the synthesis of quaternary ammonium group ion-exchange fibre, characterizes and Study on adsorption properties to Cr (VI) with glycidyl trimethylammonium chloride generation graft reaction, Zhengzhou University, 2011.].Shi Zuxia etc. prepare graft copolymer by Electron beam pre-irradiation polypropylene non-woven fabric grafted ethene yl pyridines, then graft copolymer reacts with quaternizing agent bromoethane further, prepare quaternary strongly basic anion ion exchange fibre [Shi Fuxia etc., the radiation graft process preparation of strongly basic anion ion exchange fibre and the absorption to rhenium (VII), polymer material science and engineering 2013,29 (7) 157-160.].Virendra Kumar etc. prepares anionite [V.Kumar et.al. with gossypin grafted ethene benzyltrimethylammonium chloride (VBTAC), Preparation of an anion-exchange adsorbent by the radiation-induced grafting of vinylbenzyltrimethylammonium chloride onto cotton cellulose and its application for protein adsorption, Journal of applied polymer science 2006,102 (6) 5512-5521.].Li Hai waits quietly adopting the method for high-energy irradiation DMC, DAC to be grafted on PP-g-AA fiber, [Li Hai waits quietly obtained strong basic ion exchange fiber, containing the preparation research of quaternary ammonium group ion-exchange fibre, ion-exchange and absorption 2009,25 (6) 542-549.].The fiber ubiquity percent grafting that these methods obtain is low, and adsorption capacity is little, the shortcoming that the rate of adsorption is slower, and only rests on experimental stage at present, not yet industrialization.
Summary of the invention
For the deficiencies in the prior art, the technical problem that quasi-solution of the present invention is determined is the problems such as the use of strong carcinogen in commercially available fiber-based material preparation process and technique is loaded down with trivial details, and it is little not use the technique of strong carcinogen to there is adsorption capacity, the shortcoming that the rate of adsorption is slower.The method of head it off of the present invention selects to be easy to monomer-grafted on fiber base material containing double bond and amido of grafting, then carry out quaterisation.
The invention provides a kind of fibrous material of the quick removal heavy metal anion that can be recycled, it is characterized in that raw material components and mass percent are:
Fiber base material 35%-80%
Containing the monomer 10%-37% of double bond and tertiary amine groups
1-brominated alkanes 5%-30%.
Fiber Materials of the present invention is one or more the mixture in polypropylene, Kynoar, polytetrafluoroethylene (PTFE), polysulfones, polyamide, polyvinyl chloride, polyethylene, polyacrylonitrile, PET, polyvinyl formal.The described monomer containing double bond and tertiary amine groups is methacrylic acid N, N-dimethylaminoethyl, methacrylic acid N, N-lignocaine second fat, t-butylaminoethyl methacrylate.Described 1-brominated alkanes is Celfume, bromic ether, 1-n-propyl bromide, 1-bromination of n-butane, 1-bromo pentane, 1-bromo n-hexane, 1-bromo heptane, 1-n-octane bromide, 1-bromo n-nonane, 1-bromo n-decane, 1-bromo n-undecane, 1-N-dodeeyl bromide.
The present invention aims to provide a kind of fibrous material of the quick removal heavy metal anion that can be recycled, and it is characterized in that step is as follows:
A) monomer solution containing double bond and tertiary amine groups that mass percent is 10% ~ 99% is prepared, fiber base material is put into the monomer solution containing double bond and tertiary amine groups, the mass percent of fiber base material and monomer solution is 1: 5 ~ 1: 20, after fiber base material infiltrates 2 ~ 24 hours, pass into nitrogen, irradiation Inducing Graft Polymerization, reacted fiber base material is washed, drying, obtains the fibrous material of grafting tertiary amine groups;
B) fibrous material of grafting tertiary amine groups a) obtained for step is put into the 1-brominated alkanes solution that mass percent is 10% ~ 60%, the mass percent of fibrous material and solvent is 1: 30 ~ 1: 80, be heated to 70 ~ 120 DEG C of reactions 2 ~ 7 hours under nitrogen protection, after reaction terminates, fiber is taken out, washing, dry, obtain the quaternised fibrous material of bromo;
C) by step b) the quaternised fibrous material of bromo prepared, Static Adsorption is carried out to the heavy metal anion of 1 ~ 1000mg/L, the bromo quaternized cellulose material of Adsorption of Heavy Metals anion strippant is soaked 1 ~ 4 hour, obtain regeneration bromo quaternized cellulose material, desorption efficiency reaches 85.1 ~ 99.9%;
D) by step b) the quaternised fibrous material of bromo prepared, Static Adsorption is carried out to the pentavalent arsenic solution of 1 ~ 1000mg/L, the bromo quaternized cellulose material of absorption pentavalent arsenic is soaked 1 ~ 4 hour with strippant, obtain regeneration bromo quaternized cellulose material, desorption efficiency reaches 80.1 ~ 99.9%;
E) by step b) the quaternised fibrous material of bromo prepared is according to the filling parallel with packed column inwall of fibre bundle direction, then by packed column closed at both ends, the heavy metal anion of 1 ~ 1000mg/L or pentavalent arsenic solution are passed through this packed column with the flow velocity of 0.5 ~ 10ml/min, the solution concentration at column outlet place can reach 0 ~ 0.9mg/L, bromo quaternized cellulose material strippant after absorption is passed through this packed column with the flow velocity of 0.5 ~ 10ml/min, obtain the bromo quaternized cellulose material regenerated, desorption efficiency reaches 85.1 ~ 99.9%;
F) step c can be repeated with the bromo quaternized cellulose material of regeneration) or d) or e).
Described irradiation of the present invention causes as electron beam, ultraviolet light, gamma-rays, plasma cause; Irradiance method can select pre-irradiation method or solwution method; Exposure time is 5-10 minute, and irradiation dose is 20-100kGy.Described quaternized solvent is ethanol, methyl alcohol or acetone; Described strippant is one or more the mixture in NaOH, potassium hydroxide, ammoniacal liquor, ammonium chloride, sodium chloride, potassium chloride; Described heavy metal anion is Cr VI, sexavalence tungsten, sexavalence molybdenum, pentavalent vanadium.
It is provided by the invention that what can be recycled can the functional fiber of removal heavy metal anion fast be adopt the method for irradiation by containing double bond and amido monomer-grafted on fiber base material, carry out quaterisation again, simplify reactions steps, avoid the use of strong carcinogen.The quaternary ammonium group group contained in described functional fiber is easy to react with the heavy metal anion in solution, greatly improves the adsorption efficiency of heavy metal anion.Compared with prior art the present invention has the following advantages:
1, described functional fiber adopts the method for irradiation to carry out grafting, mild condition, and technique is simple, at room temperature can carry out, and avoid the use of strong carcinogen.
2, described functional fiber has the advantage that the rate of adsorption is fast, adsorption capacity is large, adsorbent amount is little, clearance is high.
3, described functional fiber is easy to be separated and regeneration, repeatedly can recycle, can be used to the heavy metal anion removed and reclaim in industrial wastewater.
Detailed description of the invention
Describe the present invention further below in conjunction with embodiment, the explanation of the invention is not limited.
The fibrous material of a kind of quick removal heavy metal anion that can be recycled of the present invention and preparation method, technical scheme is by monomer-grafted to fiber surface by containing double bond and amido of irradiation method; Again gained fiber is carried out quaternized, can obtain described can the quaternised functional fiber of bromo of removal heavy metal anion.
Embodiment 1:
Preparation mass percent is the methacrylic acid N of 90%, N-dimethylaminoethyl monomer solution, fiber base material is put into methacrylic acid N, in N-dimethylaminoethyl monomer solution, the mass percent of fiber base material and monomer solution is 1: 20, after fiber base material infiltrates 24 hours, pass into nitrogen, adopt high-power electron beam to carry out irradiation by irradiation dose 80KGy, reacted fiber base material is washed, drying, obtains the fibrous material that percent grafting is the grafting tertiary amine groups of 56.9%.The fibrous material of obtained grafting tertiary amine groups is put into the 1-bromination of n-butane solution that mass percent is 20%; the mass percent of fibrous material and solvent is 1: 30; be heated to 70 DEG C of reactions 7 hours under nitrogen protection; after reaction terminates; fiber is taken out; washing, dry, obtain the quaternised fibrous material of bromo.
Get the quaternised fibrous material of bromo prepared by 0.5g, be placed in As (V) solution of Cr (VI) that 100mL initial concentration is 100mg/L and 10mg/L, adsorb at 25 DEG C.When 4min, clearance can reach 98.6% and 96.3%, and equilibrium adsorption capacity can reach 34.2mg/g and 3.2mg/g.
Get the quaternised fibrous material 0.2g of bromo of preparation, one end filamentary silver is fixed, and the other end, through packed column, makes fibre bundle direction parallel with filling post jamb, then takes off filamentary silver, obtain the packed column of filling the quaternized functional fiber of normal-butyl.Be that Cr (VI) solution of 100mg/L passes through packed column with the speed of 2ml/min by initial concentration, when initial 110ml, column outlet place concentration is 0, along with adsorbent solution volume increases, the ion concentration flowed out in solution increases gradually, and when 250ml, column outlet place concentration is identical with porch concentration.
To adsorb the normal-butyl quaternised Functional Chemical Fibers Wesy 0.5mol/LKOH-NaCl desorb after Cr (VI), desorption efficiency can reach 99.5%.Fiber after desorb re-starts absorption, and in 20 times, adsorption effect is substantially constant.
Embodiment 2:
Preparation mass percent is the methacrylic acid N of 80%, the N-lignocaine second alicyclic monomer aqueous solution, fiber base material is put into methacrylic acid N, in the N-lignocaine second alicyclic monomer aqueous solution, the mass percent of fiber base material and monomer solution is 1: 5, after fiber base material infiltrates 12 hours, pass into nitrogen, adopt high-power electron beam to carry out irradiation by irradiation dose 40KGy, reacted fiber base material is washed, drying, obtains the fibrous material that percent grafting is the grafting tertiary amine groups of 25.8%.The fibrous material of obtained grafting tertiary amine groups is put into the 1-n-octane bromide solution that mass percent is 60%; the mass percent of fibrous material and solvent is 1: 80; be heated to 120 DEG C of reactions 4 hours under nitrogen protection; after reaction terminates; fiber is taken out; washing, dry, obtain the quaternised fibrous material of bromo.
Get the quaternised fibrous material of n-octyl prepared by 0.1g, be placed in As (V) solution of Cr (VI) that 100mL initial concentration is 10mg/L and 10mg/L, adsorb at 25 DEG C.When 10min, clearance can reach 95.5% and 90.2%, and equilibrium adsorption capacity can reach 30.8mg/g and 2.9mg/g.
Get the quaternised fibrous material 0.1g of n-octyl of preparation, one end filamentary silver is fixed, and the other end, through packed column, makes fibre bundle direction parallel with filling post jamb, then takes off filamentary silver, obtain the packed column of filling the quaternized functional fiber of n-octyl.Be that Cr (VI) solution of 0.5mg/L passes through packed column with the speed of 5ml/min by initial concentration, when initial 1500ml, column outlet place concentration is 0, along with adsorbent solution volume increases, the ion concentration flowed out in solution increases gradually, and when 4500ml, column outlet place concentration is identical with porch concentration.
To adsorb the n-octyl quaternised fibrous material 0.5mol/LNaOH-KCl desorb after Cr (VI), desorption efficiency can reach 96.9%.Fiber after desorb re-starts absorption, and in 20 times, adsorption effect is substantially constant.
Embodiment 3:
Preparation mass percent is the methacrylic acid t-butylaminoethyl monomer solution of 70%, fiber base material is put into methacrylic acid t-butylaminoethyl monomer solution, the mass percent of fiber base material and monomer solution is 1: 20, after fiber base material infiltrates 8 hours, pass into nitrogen, gamma-rays is adopted to carry out irradiation by irradiation dose 40KGy, reacted fiber base material is washed, drying, obtains the fibrous material that percent grafting is the grafting tertiary amine groups of 45.6%.The fibrous material of obtained grafting tertiary amine groups is put into the 1-N-dodeeyl bromide solution that mass percent is 40%; the mass percent of fibrous material and solvent is 1: 60; be heated to 80 DEG C of reactions 6 hours under nitrogen protection; after reaction terminates; fiber is taken out; washing, dry, obtain the quaternised fibrous material of bromo.
Get the quaternised fibrous material of dodecyl prepared by 0.3g, be placed in As (V) solution of Cr (VI) that 100mL initial concentration is 100mg/L and 10mg/L, adsorb at 25 DEG C.When 30min, clearance can reach 87.9% and 85.1%, and equilibrium adsorption capacity can reach 25.3mg/g and 2.5mg/g.
Get the quaternised fibrous material 0.1g of dodecyl of preparation, one end filamentary silver is fixed, and the other end, through packed column, makes fibre bundle direction parallel with filling post jamb, then takes off filamentary silver, obtain the packed column of filling the quaternized functional fiber of dodecyl.Be that As (V) solution of 0.5mg/L passes through packed column with the speed of 5ml/min by initial concentration, when initial 1450ml, column outlet place concentration is 0, along with adsorbent solution volume increases, the ion concentration flowed out in solution increases gradually, and when 4500ml, column outlet place concentration is identical with porch concentration.
To adsorb the dodecyl quaternised fibrous material 0.5mol/LNaOH-NaCl desorb after As (V), desorption efficiency can reach 95.1%.Fiber after desorb re-starts absorption, and in 20 times, adsorption effect is substantially constant.
Embodiment 4:
Polypropylene fibre is put into the ethanolic solution containing 0.5% benzophenone, soak taking-up in 7 hours, dry in the shade.Preparation mass percent is the methacrylic acid N of 70%, N-dimethylaminoethyl monomer solution, fiber base material is put into methacrylic acid N, in N-dimethylaminoethyl monomer solution, the mass percent of fiber base material and monomer solution is 1: 10, after fiber base material infiltrates 12 hours, pass into nitrogen, be 1000W at power, wavelength is irradiation in the ultraviolet radiation facility of 365nm, and reacted fiber base material washs by irradiation 20min, drying, obtains the fibrous material that percent grafting is the grafting tertiary amine groups of 22.8%.The fibrous material of obtained grafting tertiary amine groups is put into the bromic ether solution that mass percent is 60%; the mass percent of fibrous material and solvent is 1: 60; be heated to 85 DEG C of reactions 3 hours under nitrogen protection; after reaction terminates; fiber is taken out; washing, dry, obtain the quaternised fibrous material of bromo.
Get the quaternised fibrous material of ethyl group prepared by 0.3g, be placed in W (VI) solution that 100mL initial concentration is 10mg/L, adsorb at 25 DEG C.When 6min, clearance can reach 91.0%, and equilibrium adsorption capacity can reach 2.9mg/g.
Get the quaternised fibrous material 0.2g of ethyl group of preparation, one end filamentary silver is fixed, and the other end, through packed column, makes fibre bundle direction parallel with filling post jamb, then takes off filamentary silver, obtain the packed column of filling the quaternized functional fiber of ethyl group.Be that W (VI) solution of 1mg/L passes through packed column with the speed of 5ml/min by initial concentration, when initial 2750ml, column outlet place concentration is 0, along with adsorbent solution volume increases, the ion concentration flowed out in solution increases gradually, and when 6800ml, column outlet place concentration is identical with porch concentration.
By the quaternised fibrous material NH of ethyl group adsorbed after W (VI)
3-NH
4cl desorb, desorption efficiency can reach 98.9%.Fiber after desorb re-starts absorption, and in 20 times, adsorption effect is substantially constant.
Embodiment 5:
Fiber is put into the ethanolic solution containing 0.1% benzophenone, soak taking-up in 7 hours, dry in the shade.Preparation mass percent is the methacrylic acid N of 20%, and N-dimethylaminoethyl monomer solution, puts into methacrylic acid N by fiber base material, in N-dimethylaminoethyl monomer solution, the mass percent of fiber base material and monomer solution is 1: 15, after fiber base material infiltrates 20 hours, passes into nitrogen, be 1000W at power, wavelength is irradiation in the ultraviolet radiation facility of 365nm, and reacted fiber base material washs by irradiation 5min, drying, obtains the fibrous material of grafting tertiary amine groups.The fibrous material of obtained grafting tertiary amine groups is put into the 1-bromo hexane solution that mass percent is 10%; the mass percent of fibrous material and solvent is 1: 60; be heated to 95 DEG C of reactions 9 hours under nitrogen protection; after reaction terminates; fiber is taken out; washing, dry, obtain the quaternised fibrous material of bromo.
Get the quaternised fibrous material of n-hexane base prepared by 0.3g, be placed in V (V) solution that 100mL initial concentration is 10mg/L, adsorb at 25 DEG C.91.0%, equilibrium adsorption capacity can reach 3.2mg/g.
Get the quaternised fibrous material 0.2g of n-hexane base of preparation, one end filamentary silver is fixed, and the other end, through packed column, makes fibre bundle direction parallel with filling post jamb, then takes off filamentary silver, obtain the packed column of filling the quaternized functional fiber of n-hexane base.Be that V (V) solution of 10mg/L passes through packed column with the speed of 5ml/min by initial concentration, when initial 255ml, column outlet place concentration is 0, along with adsorbent solution volume increases, the ion concentration flowed out in solution increases gradually, and when 585ml, column outlet place concentration is identical with porch concentration.
To adsorb the n-hexane base quaternised fibrous material 0.5mol/LKOH-NaCl desorb after V (V), desorption efficiency can reach 99.1%.Fiber after desorb re-starts absorption, and in 20 times, adsorption effect is substantially constant.
Embodiment 6:
Preparation mass percent is the t-butylaminoethyl methacrylate monomer solution of 50%, fiber base material is put into t-butylaminoethyl methacrylate monomer solution, the mass percent of fiber base material and monomer solution is 1: 20, after fiber base material infiltrates 20 hours, logical taking-up, dry.With plasma radiation, irradiation 1min, washs reacted fiber base material, dry, obtains the fibrous material of grafting tertiary amine groups.The fibrous material of obtained grafting tertiary amine groups is put into the 1-bromo positive flow silane solution that mass percent is 60%; the mass percent of fibrous material and solvent is 1: 40; be heated to 105 DEG C of reactions 7 hours under nitrogen protection; after reaction terminates; fiber is taken out; washing, dry, obtain the quaternised fibrous material of bromo.
Get the quaternised fibrous material of positive flow silane base prepared by 0.3g, be placed in Mo (VI) solution that 100mL initial concentration is 10mg/L, adsorb at 25 DEG C.When 30min, clearance can reach 92.2%, and equilibrium adsorption capacity can reach 2.6mg/g.
Get the quaternised fibrous material 0.2g of positive flow silane base of preparation, one end filamentary silver is fixed, and the other end, through packed column, makes fibre bundle direction parallel with filling post jamb, then takes off filamentary silver, obtain the packed column of filling the quaternized functional fiber of positive flow silane base.Be that Mo (VI) solution of 1mg/L passes through packed column with the speed of 5ml/min by initial concentration, when initial 2245ml, column outlet place concentration is 0, along with adsorbent solution volume increases, the ion concentration flowed out in solution increases gradually, and when 5985ml, column outlet place concentration is identical with porch concentration.
By the quaternised fibrous material NH of positive flow silane base adsorbed after Mo (VI)
3-NH
4cl desorb, desorption efficiency can reach 96.2%.Fiber after desorb re-starts absorption, and in 20 times, adsorption effect is substantially constant.
Claims (9)
1. a fibrous material for the quick removal heavy metal anion that can be recycled, is characterized in that raw material components and mass percent are:
Fiber base material 35%-80%
Containing the monomer 10%-37% of double bond and tertiary amine groups
1-brominated alkanes 5%-30%.
2. a fibrous material for the quick removal heavy metal anion that can be recycled, is characterized in that step is as follows:
A) monomer solution containing double bond and tertiary amine groups that mass percent is 10% ~ 99% is prepared, fiber base material is put into the monomer solution containing double bond and tertiary amine groups, the mass percent of fiber base material and monomer solution is 1: 5 ~ 1: 20, after fiber base material infiltrates 2 ~ 24 hours, pass into nitrogen, irradiation Inducing Graft Polymerization, reacted fiber base material is washed, drying, obtains the fibrous material of grafting tertiary amine groups;
B) fibrous material of grafting tertiary amine groups a) obtained for step is put into the 1-brominated alkanes solution that mass percent is 10% ~ 60%, the mass percent of fibrous material and solvent is 1: 30 ~ 1: 80, be heated to 70 ~ 120 DEG C of reactions 2 ~ 7 hours under nitrogen protection, after reaction terminates, fiber is taken out, washing, dry, obtain the quaternised fibrous material of bromo;
C) by step b) the quaternised fibrous material of bromo prepared, Static Adsorption is carried out to the heavy metal anion of 1 ~ 1000mg/L, the bromo quaternized cellulose material of Adsorption of Heavy Metals anion strippant is soaked 1 ~ 4 hour, obtain regeneration bromo quaternized cellulose material, desorption efficiency reaches 85.1 ~ 99.9%;
D) by step b) the quaternised fibrous material of bromo prepared, Static Adsorption is carried out to the pentavalent arsenic solution of 1 ~ 1000mg/L, the bromo quaternized cellulose material of absorption pentavalent arsenic is soaked 1 ~ 4 hour with strippant, obtain regeneration bromo quaternized cellulose material, desorption efficiency reaches 80.1 ~ 99.9%;
E) by step b) the quaternised fibrous material of bromo prepared is according to the filling parallel with packed column inwall of fibre bundle direction, then by packed column closed at both ends, the heavy metal anion of 1 ~ 1000mg/L or pentavalent arsenic solution are passed through this packed column with the flow velocity of 0.5 ~ 10ml/min, the solution concentration at column outlet place can reach 0 ~ 0.9mg/L, bromo quaternized cellulose material strippant after absorption is passed through this packed column with the flow velocity of 0.5 ~ 10ml/min, obtain the bromo quaternized cellulose material regenerated, desorption efficiency reaches 85.1 ~ 99.9%;
F) step c can be repeated with the bromo quaternized cellulose material of regeneration) or d) or e).
3. the fibrous material of a kind of quick removal heavy metal anion that can be recycled as claimed in claim 1, is characterized in that described Fiber Materials is one or more the mixture in polypropylene, Kynoar, polytetrafluoroethylene (PTFE), polysulfones, polyamide, polyvinyl chloride, polyethylene, polyacrylonitrile, PET, polyvinyl formal.
4. the fibrous material of a kind of quick removal heavy metal anion that can be recycled as claimed in claim 1, it is characterized in that the described monomer containing double bond and tertiary amino is methacrylic acid N, N-dimethylaminoethyl, methacrylic acid N, N-lignocaine second fat, t-butylaminoethyl methacrylate.
5. the fibrous material of a kind of quick removal heavy metal anion that can be recycled as claimed in claim 1, is characterized in that described 1-brominated alkanes is Celfume, bromic ether, 1-n-propyl bromide, 1-bromination of n-butane, 1-bromo pentane, 1-bromo n-hexane, 1-bromo heptane, 1-n-octane bromide, 1-bromo n-nonane, 1-bromo n-decane, 1-bromo n-undecane, 1-N-dodeeyl bromide.
6. the fibrous material of a kind of quick removal heavy metal anion that can be recycled as claimed in claim 2, is characterized in that described irradiation causes as electron beam, ultraviolet light, gamma-rays, plasma cause.
7. the fibrous material of a kind of quick removal heavy metal anion that can be recycled as claimed in claim 2, is characterized in that step b) described in solvent be methyl alcohol, ethanol or acetone.
8. the fibrous material of a kind of quick removal heavy metal anion that can be recycled as claimed in claim 2, is characterized in that described strippant is one or more the mixture in NaOH, potassium hydroxide, ammoniacal liquor, ammonium chloride, sodium chloride, potassium chloride.
9. the fibrous material of a kind of quick removal heavy metal anion that can be recycled as claimed in claim 2, is characterized in that described heavy metal anion is Cr VI, sexavalence tungsten, sexavalence molybdenum, pentavalent vanadium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510311532.1A CN104941588A (en) | 2015-06-01 | 2015-06-01 | Recyclable fiber material capable of quickly removing heavy metal anions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510311532.1A CN104941588A (en) | 2015-06-01 | 2015-06-01 | Recyclable fiber material capable of quickly removing heavy metal anions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104941588A true CN104941588A (en) | 2015-09-30 |
Family
ID=54156959
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510311532.1A Pending CN104941588A (en) | 2015-06-01 | 2015-06-01 | Recyclable fiber material capable of quickly removing heavy metal anions |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104941588A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105817210A (en) * | 2016-05-24 | 2016-08-03 | 马鞍山中创环保科技有限公司 | Method for preparing alkalescent ion exchange fibers |
| CN105999406A (en) * | 2016-06-02 | 2016-10-12 | 温州医科大学 | Method for preparing high-efficiency antibacterial quaternary ammonium salt chitosan composite gel coating layer |
| CN108380186A (en) * | 2018-01-12 | 2018-08-10 | 中国地质大学（武汉） | It is a kind of to recycle Cr (VI) adsorbent and preparation method thereof haveing excellent performance |
| CN110026159A (en) * | 2019-04-29 | 2019-07-19 | 广西科技师范学院 | A kind of preparation method of lead adsorbent |
| CN110404518A (en) * | 2018-04-27 | 2019-11-05 | 天津瀚德新材料科技有限公司 | Preparation method for the polyfunctional group fibre enrichment combined diaphragm of heavy metal ion in X-ray fluorescence spectra detection water |
| CN110860277A (en) * | 2019-12-09 | 2020-03-06 | 天津工业大学 | Method for extracting rare earth metal from aminodiacetic acid modified fiber |
| CN112593403A (en) * | 2020-11-28 | 2021-04-02 | 郑州大学 | Preparation method of polyacrylonitrile-based strong base ion exchange fiber |
| CN112604674A (en) * | 2020-12-10 | 2021-04-06 | 重庆科技学院 | Fiber-based adsorption material, preparation method thereof and removal of trivalent chromium in water body |
| CN114703661A (en) * | 2022-03-17 | 2022-07-05 | 宜兴市凯斯特环保机械有限公司 | Strong base type ion exchange fiber and preparation method thereof |
| CN115198524A (en) * | 2022-06-27 | 2022-10-18 | 安徽农业大学 | Quaternary ammonium salt functionalized fiber with hydrophilic group and preparation method and application thereof |
| CN116531848A (en) * | 2023-06-26 | 2023-08-04 | 江苏奥凯环境技术有限公司 | Colored aramid fiber filter material for flue gas purification and production process thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1584188A (en) * | 2004-06-11 | 2005-02-23 | 上海大学 | Preparing method for temperature controlling ionic absorbing fibre |
| US20080053922A1 (en) * | 2006-09-01 | 2008-03-06 | Honsinger Charles P Jr | Nanostructured materials comprising support fibers coated with metal containing compounds and methods of using the same |
| CN101543795A (en) * | 2008-03-26 | 2009-09-30 | 财团法人工业技术研究院 | Ion exchange material with adsorption function and method for filtering heavy metal ions by using material |
| CN101768865A (en) * | 2009-11-26 | 2010-07-07 | 天津工业大学 | Preparation method of ion-exchange fibre containing carboxyl and quaternary ammonium group |
| CN102962040A (en) * | 2012-12-19 | 2013-03-13 | 天津工业大学 | Molecularly imprinted membrane for chiral separation and preparation method thereof |
-
2015
- 2015-06-01 CN CN201510311532.1A patent/CN104941588A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1584188A (en) * | 2004-06-11 | 2005-02-23 | 上海大学 | Preparing method for temperature controlling ionic absorbing fibre |
| US20080053922A1 (en) * | 2006-09-01 | 2008-03-06 | Honsinger Charles P Jr | Nanostructured materials comprising support fibers coated with metal containing compounds and methods of using the same |
| CN101543795A (en) * | 2008-03-26 | 2009-09-30 | 财团法人工业技术研究院 | Ion exchange material with adsorption function and method for filtering heavy metal ions by using material |
| CN101768865A (en) * | 2009-11-26 | 2010-07-07 | 天津工业大学 | Preparation method of ion-exchange fibre containing carboxyl and quaternary ammonium group |
| CN102962040A (en) * | 2012-12-19 | 2013-03-13 | 天津工业大学 | Molecularly imprinted membrane for chiral separation and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| ZHI-YUN KONG ET AL.,: ""Rapid removal of Cr(VI) ions using quaternary ammonium fibers functioned by 2-(dimethylamino)ethyl methacrylate and modified with 1-bromoalkanes"", 《CHEMICAL ENGINEERING JOURNAL》 * |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105817210A (en) * | 2016-05-24 | 2016-08-03 | 马鞍山中创环保科技有限公司 | Method for preparing alkalescent ion exchange fibers |
| CN105999406A (en) * | 2016-06-02 | 2016-10-12 | 温州医科大学 | Method for preparing high-efficiency antibacterial quaternary ammonium salt chitosan composite gel coating layer |
| CN108380186B (en) * | 2018-01-12 | 2020-08-25 | 中国地质大学（武汉） | Cr (VI) adsorbent with excellent recycling performance and preparation method thereof |
| CN108380186A (en) * | 2018-01-12 | 2018-08-10 | 中国地质大学（武汉） | It is a kind of to recycle Cr (VI) adsorbent and preparation method thereof haveing excellent performance |
| CN110404518A (en) * | 2018-04-27 | 2019-11-05 | 天津瀚德新材料科技有限公司 | Preparation method for the polyfunctional group fibre enrichment combined diaphragm of heavy metal ion in X-ray fluorescence spectra detection water |
| CN110026159A (en) * | 2019-04-29 | 2019-07-19 | 广西科技师范学院 | A kind of preparation method of lead adsorbent |
| CN110860277A (en) * | 2019-12-09 | 2020-03-06 | 天津工业大学 | Method for extracting rare earth metal from aminodiacetic acid modified fiber |
| CN112593403A (en) * | 2020-11-28 | 2021-04-02 | 郑州大学 | Preparation method of polyacrylonitrile-based strong base ion exchange fiber |
| CN112593403B (en) * | 2020-11-28 | 2022-06-03 | 郑州大学 | Preparation method of polyacrylonitrile-based strong base ion exchange fiber |
| CN112604674A (en) * | 2020-12-10 | 2021-04-06 | 重庆科技学院 | Fiber-based adsorption material, preparation method thereof and removal of trivalent chromium in water body |
| CN114703661A (en) * | 2022-03-17 | 2022-07-05 | 宜兴市凯斯特环保机械有限公司 | Strong base type ion exchange fiber and preparation method thereof |
| CN115198524A (en) * | 2022-06-27 | 2022-10-18 | 安徽农业大学 | Quaternary ammonium salt functionalized fiber with hydrophilic group and preparation method and application thereof |
| CN116531848A (en) * | 2023-06-26 | 2023-08-04 | 江苏奥凯环境技术有限公司 | Colored aramid fiber filter material for flue gas purification and production process thereof |
| CN116531848B (en) * | 2023-06-26 | 2023-09-12 | 江苏奥凯环境技术有限公司 | Colored aramid fiber filter material for flue gas purification and production process thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104941588A (en) | Recyclable fiber material capable of quickly removing heavy metal anions | |
| Dong et al. | Covalently bonded ionic liquid onto cellulose for fast adsorption and efficient separation of Cr (VI): Batch, column and mechanism investigation | |
| Usman et al. | Simultaneous adsorption of heavy metals and organic dyes by β-Cyclodextrin-Chitosan based cross-linked adsorbent | |
| Min et al. | Micro-nano structure poly (ether sulfones)/poly (ethyleneimine) nanofibrous affinity membranes for adsorption of anionic dyes and heavy metal ions in aqueous solution | |
| Selambakkannu et al. | A kinetic and mechanistic study of adsorptive removal of metal ions by imidazole-functionalized polymer graft banana fiber | |
| Sokker et al. | Radiation-induced grafting of glycidyl methacrylate onto cotton fabric waste and its modification for anchoring hazardous wastes from their solutions | |
| Sekine et al. | Biodegradable metal adsorbent synthesized by graft polymerization onto nonwoven cotton fabric | |
| Li et al. | Crosslinked chitosan nanofiber mats fabricated by one-step electrospinning and ion-imprinting methods for metal ions adsorption | |
| CN104587956B (en) | A kind of preparation method being coated with the graphene oxide composite granule coated nano zero valence iron as carrier with multilamellar activated carbon | |
| CN106076290B (en) | A kind of method and application of the quick modified acrylic fibre of microwave | |
| CN107262060A (en) | A kind of heavy metal ion adsorbing material and preparation method thereof | |
| Pan et al. | Novel sulfhydryl functionalized covalent organic frameworks for ultra-trace Hg2+ removal from aqueous solution | |
| Kavaklı et al. | Preparation of quaternized dimethylaminoethylmethacrylate grafted nonwoven fabric for the removal of phosphate | |
| CN107262061A (en) | A kind of heavy metal ion adsorbing material based on graphene and preparation method thereof | |
| CN106215910A (en) | A kind of preparation method of acid cation exchange fiber | |
| WO2018129859A1 (en) | Preparation method, regeneration method and application for chelating microfiltration membrane | |
| CN103495399B (en) | Preparation method and application of sludge activated carbon | |
| CN103159891A (en) | Magnetic amino-modified superhighly-crosslinked resin and preparation method thereof | |
| CN106492591B (en) | The exploitation of concentration runner and its application in VOCs improvement | |
| Ting et al. | Modification of polyethylene-polypropylene fibers by emulsion and solvent radiation grafting systems for boron removal | |
| Valderrama et al. | Evaluation of hyper-cross-linked polymeric sorbents (Macronet MN200 and MN300) on dye (Acid red 14) removal process | |
| CN111359585A (en) | Ionic liquid covalent bonding immobilized silicon-based material, preparation method and application thereof | |
| Laureano-Anzaldo et al. | Plasma-enhanced modification of polysaccharides for wastewater treatment: A review | |
| Kim et al. | Separation of valuables from spent selective catalytic reduction catalyst leaching solution by fabricated anion extraction resins | |
| Zhang et al. | Method to fabricate porous multifunction β-cyclodextrin modified resin for ultrafast and efficient removal of Cu (II) and bisphenol A |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20150930 |