CN106732456A - Triethylene tetramine crosslinked chitosan resin of quaternary ammonium fundamental mode and preparation method thereof - Google Patents

Triethylene tetramine crosslinked chitosan resin of quaternary ammonium fundamental mode and preparation method thereof Download PDF

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CN106732456A
CN106732456A CN201611167786.1A CN201611167786A CN106732456A CN 106732456 A CN106732456 A CN 106732456A CN 201611167786 A CN201611167786 A CN 201611167786A CN 106732456 A CN106732456 A CN 106732456A
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shitosan
triethylene tetramine
crosslinked chitosan
quaternary ammonium
chitosan resin
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CN106732456B (en
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李昱
谭颂
秦礼星
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HUBEI ACADEMY OF ENVIRONMENTAL SCIENCES
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
    • B01J20/267—Cross-linked polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

Triethylene tetramine crosslinked chitosan resin the present invention relates to quaternary ammonium fundamental mode and preparation method thereof.The aqueous acetic acid of shitosan, atoleine, the dispersions of Span 80 are formed into water-in-oil type reversed-phase emulsion; amido protection shitosan is obtained with formalin reaction; reaction solution adjusts pH; epoxychloropropane is allowed to protect chitosan reaction with above-mentioned amido; suction filtration, washing is extracted; dry, obtain the shitosan of Epichlorohydrin activation；Immersion, is heated up, and adds triethylene tetramine to be crosslinked, and filters, and washing is extracted, and is dried, and obtains triethylene tetramine crosslinked chitosan resin；Allow epoxypropyltrimethylchloride chloride to react, filter, washing is drying to obtain.The invention has the advantages that：(1) with good permeability, mechanical performance and resistance to acids and bases.(2) can be applied to the adsorption treatment of waste water.Particularly, to contents of many kinds of heavy metal ion such as vanadium, chromium, the arsenic in the percolate waste water of navajoite smelting tailing storehouse with excellent absorption property.

Description

Triethylene tetramine crosslinked chitosan resin of quaternary ammonium fundamental mode and preparation method thereof
Technical field
The present invention relates to chelating resin and its synthetic method, belong to technical field of adsorbent resins, specifically a kind of season Triethylene tetramine crosslinked chitosan resin of ammonium type and preparation method thereof.
Background technology
With the fast development of industry, caused by the heavy metal and organic pollution in industrial wastewater, environmental pollution is increasingly Seriously, the prevention and control of water pollution are also increasingly paid attention to for government and relevant departments.Particularly, in order to effectively remove industrial wastewater Exceeded heavy metal pollution, absorption method obtains most commonly used application as a kind of simple effective method.As absorption method most An important link is exactly the exploitation of sorbing material and is used.
In numerous sorbing materials, the research and development of shitosan class sorbing material receive universal concern, and this is mainly base In following three advantages：1) from the structure of compound, shitosan is that glycosaminoglycan is birdsed of the same feather flock together compound, and intramolecular contains largely Amino and the complexing such as hydroxyl site (amino for particularly wherein containing), the chelating of stabilization can be formed with metal ion etc. Thing, therefore adsorption capacity high is shown to metal ion etc.；2) from the point of view of financial cost, shitosan is chitin in alkaline bar Product under part after deacetylation, its raw material chitin is the second largest polysaccharide that content is only second to cellulose, is mainly derived from water Product processing waste material, for example, eat up shrimp shell crab shell of lobster and crab etc., therefore, shitosan has wide material sources and production cost Low huge advantage；3) shitosan has nontoxic, biodegradable and reproducible advantage, is preferable environment-friendly materials.Additionally, Amino and hydroxyl have good reactivity, can as needed carry out chemical modification, the more excellent sorbing material of exploitation performance.
But, it is linear soft high molecular polymer without the shitosan of chemical modification, it is past in acid medium Toward meeting because of the-NH in molecule2Protonated amino (- NH3 +) and improve its water solubility, the loss of adsorbent is easily caused, stability It is poor；Meanwhile, shitosan also has the shortcomings that mechanical performance is bad and porosity is low.These all limit the application of shitosan. Therefore, in order to overcome these unfavorable conditions, can be from the chemical property (degree of cross linking and function of molecular structure of shitosan class material The species of base, number and density) and the aspect of physical property (particle diameter, porosity and specific surface area) two be modified research.
The content of the invention
Problem to be solved by this invention is to provide a kind of quaternary ammonium fundamental mode triethylene tetramine crosslinked chitosan resin and its system Preparation Method, it reacts shitosan by reversed-phase emulsion, and triethylene tetramine is not only obtained on the basis of Epichlorohydrin activation Crosslinked chitosan resin, and grafting introduces quaternary ammonium group on the polymer side chain of crosslinked chitosan resin, considerably increases Resin makes the purposes of the resin more to heavy metal cation in complicated solution and the absorption property of heavy metal Oxoanions Extensively, it is in hgher efficiency.
In order to solve the above problems, the invention provides a kind of quaternary ammonium fundamental mode triethylene tetramine crosslinked chitosan resin, its Structural formula is as follows：
The preparation method of quaternary ammonium fundamental mode triethylene tetramine crosslinked chitosan resin is as follows：
By aqueous acetic acid that mass fraction is 5% shitosan, atoleine, that the dispersions of Span 80 form water-in-oil type is anti- Phase emulsion, obtains amido protection shitosan for 1-2 hours at 50-70 DEG C with formalin reaction, is then adjusted to reaction solution PH=9-11, allows epoxychloropropane with above-mentioned amido protection shitosan in being reacted 2-4 hours at 60-80 DEG C, and suction filtration, washing is used Petroleum ether carries out surname extraction, dries, and obtains the shitosan of Epichlorohydrin activation；The shell of above-mentioned Epichlorohydrin activation is gathered Sugar is immersed in the aqueous solution of pH=9-10, is warming up to 50-80 DEG C, adds triethylene tetramine to be crosslinked, and is filtered, and washing is used Ethanol carries out surname extraction, dries, and obtains triethylene tetramine crosslinked chitosan resin；At 60-80 DEG C, glycidyl front three is allowed Ammonium chloride reacts 12-24 hours with above-mentioned triethylene tetramine crosslinked chitosan resin, filtering, and washing is dried to obtain quaternary ammonium salt The chitosan resin of substituted triethylene tetramine crosslinking.
The aqueous acetic acid of described shitosan is 1 with the volume ratio of atoleine:1—2:1, the throwing of formaldehyde and shitosan Plus mass ratio is 1:4—1:2, epoxychloropropane is 1 with the mass ratio that adds of shitosan:2—1:1, triethylene tetramine with it is above-mentioned The shitosan of Epichlorohydrin activation adds mass ratio 1:3—1:1, epoxypropyltrimethylchloride chloride is handed over triethylene tetramine The mass ratio that adds of connection chitosan resin is 1:30—1:5.
The synthetic route of quaternary ammonium fundamental mode triethylene tetramine crosslinked chitosan resin of the present invention is as follows：
Compared with prior art, the invention has the advantages that：
(1) the quaternary ammonium fundamental mode triethylene tetramine crosslinked chitosan resin that the present invention is obtained by antiphase emulsifiable method, does not dissolve in Water, with good permeability, mechanical performance and resistance to acids and bases.
(2) present invention makes shitosan obtain triethylene tetramine cross-linked chitosan first on the basis of Epichlorohydrin activation Resin, then remarries on polymer side chain and connects the quaternary ammonium fundamental mode triethylene tetramine cross-linked chitosan that introducing quaternary ammonium salt group is obtained Resin, due to introducing substantial amounts of amido, quaternary ammonium salt group, heavy metal ion has excellent absorption property, can be applied to The adsorption treatment of waste water.Particularly, to contents of many kinds of heavy metal ion such as vanadium, chromium, the arsenic in the percolate waste water of navajoite smelting tailing storehouse With excellent absorption property.
Specific embodiment
Embodiments of the invention are further described below, and protection scope of the present invention is not only limited in following examples.
Embodiment 1：
The chitosan-acetic acid solution that mass fraction is 5% is prepared, 10g shitosans are dissolved in the acetums of 190mL 2% In, stir and place 24 hours.The shitosan Acetate gels liquid (about 200mL) that 24 hours will be placed is transferred to tri- mouthfuls of 1000mL In flask, the addition of 167mL atoleines is measured, be warming up to 50 DEG C after mechanical agitation 15min at room temperature, drop span80 is emulsified plus 5 10min, is warming up to 60 DEG C, adds the formaldehyde of 9.74mL 36%, reacts 1 hour, and now solution is sticky is difficult agitation；Then, adjust Section pH to 10 (uses 5% NaOH solution, w/w), and now solution becomes less viscous thick, easily agitation；7.3mL epoxy chloropropionates are added dropwise Alkane, is warming up to 70 DEG C, and 5% NaOH solution is slowly added dropwise with constant pressure funnel, keeps the pH of system in 10 or so, reaction 2 Hour, suction filtration, distillation 4 times (each 300mL) of washing is obtained than more uniform light yellow clear spherical resin.Use 250mL petroleum ethers Think highly of extrct in surname extraction and remove residual organic matter (paraffin etc.) 24 hours, gained resin is put into surface plate the unnecessary stone that volatilizees Oily ether, 60 DEG C of vacuum drying.
The shitosan for taking the above-mentioned Epichlorohydrin activations of 3.0g soaks in 65 DEG C of 150mL 0.1mol/L NaOH solutions Bubble, is then slowly added dropwise 15mL triethylene tetramines thereto.Mixture stirring reaction 4 hours, then filters, successively with ethanol, , to remove unreacted triethylene tetramine, final products are obtained in 60 DEG C of vacuum drying for acetone, ether and distillation water washing The triethylene tetramine crosslinking N- benzylidene shitosans of 3.48g yellow powders.Then triethylene tetramine is crosslinked N- benzene methylenes Base enclosure glycan is soaked 24 hours in being added in the HCl solution of 2% (volume), and filtering is washed with distilled water, ethanol and ether successively Wash, then soaked 24 hours in the NaOH solution of 1% (volume).Much filtrate is dried to obtain 2.04g in the vacuum at 60 DEG C yellow The triethylene tetramine crosslinked chitosan resin of color.
Take the above-mentioned crosslinked chitosan resins of 2.0g to be scattered in 100mL distilled water, add 0.2g epoxy chlorine Change ammonium after, mixture stirring reaction 24 hours at 60 DEG C, after completion of the reaction resin distilled water fully wash to remove epoxy Hydroxypropyltrimonium chloride, 2.06g crosslinked chitosan resins (I) are obtained after drying.
Embodiment 2：
(1) for navajoite smelting tailing stock feature heavy metal be percolated pollution problem, through to heavy metal in percolate Ion test is learnt：There are various heavy metals exceeding standards in percolate, wherein vanadium concentration contains 0.5~1mg/L, mainly with vanadium Oxysalt form exist, lead, cadmium, mercury concentration between 0.1~0.2mg/L, more than surface water II class standards 20 again with On.Navajoite smelting tailing percolate raw water sample takes from Hubei extracting vanadium from stone coal smeltery in this example, is determined by with ICP-MS Vanadium, chromium, arsenic, lead and the heavy metal species ion concentration of cadmium five in raw water before absorption, before being adsorbed with Atomic Fluorescence Spectrometry raw water mercury from Sub- concentration is：
Heavy metal ion Hg(ug/l) V(ug/l) Cr(ug/l) As(ug/l) Cd(ug/l) Pb(ug/l)
Raw water sample concentration 1247 7278.636 891.61 1095.04 1075.195 1041.79
(2) the gained quaternary ammonium fundamental mode triethylene tetramine crosslinked chitosan resin 0.2g of embodiment 1 for handling well is weighed respectively to add Enter in the 250ml plastic bottles for filling 100.0ml raw water samples, placement is vibrated and starts timing on the oscillator, is in the time Taken respectively when 5min, 10min, 30min, 1h, 2h, 4h, 6h, 9h supernatant 5ml determine after its absorption mercury in solution, vanadium, chromium, The concentration of arsenic, lead and cadmium heavy metal ion, as a result see the table below (ND is not to detect)：
(3) weigh respectively handle well resin 0.0516g, 0.1055g, 0.1503g, 0.2015g, 0.3003g, 0.4012nd, 0.5077g, is added separately in the 150ml plastic bottles for fill 50.0ml raw water samples, and placement is vibrated on the oscillator 9h.Take supernatant and survey each metal concentration, as a result see the table below (ND is not to detect)：
CCTS(g) Hg(ug/l) V(ug/l) Cr(ug/l) As(ug/l) Cd(ug/l) Pb(ug/l)
0.05g 18.900 ND 2.793 5.295 92.333 84.035
0.1g - ND 3.725 3.250 91.859 87.803
0.15g 2.644 ND 3.481 2.741 93.113 85.049
0.20g 2.213 ND 3.404 2.188 91.533 80.102
0.30g 0.293 ND 1.627 1.583 85.725 39.665
0.40g 2.307 ND 1.447 1.232 83.321 40.995
0.50g 3.380 ND 0.236 1.056 69.822 3.454
Raw water 1247 7278.636 891.61 1095.04 1075.195 1041.79
Embodiment 3：
Resin (I) 0.2000g prepared by precise embodiment 1, is placed in 150mL conical flask with cover, adds configuration Heavy metal ion mixed solution 100mL, vibrates 24h in constant temperature oscillator, and absorption front and rear vanadium, chromium, arsenic, lead are determined with ICP-MS And the change of the heavy metal species ion concentration of cadmium five, the change of ion concentration of mercury before and after being adsorbed with Atomic Fluorescence Spectrometry, under Formula calculates adsorption capacity：
Q=(C0-C)V/W
Q is adsorption capacity (mg/g) in formula, and C0 and C is respectively the concentration (mg/L) of metal ion before and after absorption, and W is absorption Resin dry weight (g), V is liquor capacity (L).
Table one：The adsorption capacity (mg/g) of crosslinked chitosan resin (I)

Claims (3)

1. a kind of quaternary ammonium fundamental mode triethylene tetramine crosslinked chitosan resin, its structural formula is as follows：
2. the preparation method of the triethylene tetramine crosslinked chitosan resin of quaternary ammonium fundamental mode, it is characterised in that by mass fraction be 5% The aqueous acetic acid of shitosan, atoleine, the dispersions of Span 80 form water-in-oil type reversed-phase emulsion, with formaldehyde at 50-70 DEG C Obtain within reactant aqueous solution 1-2 hours amido protection shitosan, reaction solution is then adjusted to pH=9-11, allow epoxychloropropane with it is upper Amido protection shitosan is stated in being reacted 2-4 hours at 60-80 DEG C, suction filtration, washing carries out surname extraction with petroleum ether, dries, and obtains To the shitosan of Epichlorohydrin activation；The shitosan of above-mentioned Epichlorohydrin activation is immersed in the aqueous solution of pH=9-10 In, 50-80 DEG C is warming up to, add triethylene tetramine to be crosslinked, to filter, washing carries out surname extraction with ethanol, dries, and obtains To triethylene tetramine crosslinked chitosan resin；At 60-80 DEG C, epoxypropyltrimethylchloride chloride and above-mentioned triethylene tetramine are allowed Crosslinked chitosan resin reacts 12-24 hours, filtering, washing, is dried to obtain the shell of the triethylene tetramine crosslinking of quaternary ammonium salt substitution Polysaccharide resins.
3. the preparation method of the triethylene tetramine crosslinked chitosan resin of the quaternary ammonium fundamental mode as described in claim 2, its feature exists In the volume ratio of aqueous acetic acid and the atoleine of shitosan be 1:1—2:1, formaldehyde is 1 with the mass ratio that adds of shitosan: 4—1:2, epoxychloropropane is 1 with the mass ratio that adds of shitosan:2—1:1, triethylene tetramine is lived with above-mentioned epoxychloropropane The shitosan of change adds mass ratio 1:3—1:1, epoxypropyltrimethylchloride chloride and triethylene tetramine crosslinked chitosan resin Add mass ratio for 1:30—1:5.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107804905A (en) * 2017-10-27 2018-03-16 广州安达净水材料有限公司 A kind of organic coagulants and preparation method thereof
WO2020199738A1 (en) * 2019-04-04 2020-10-08 中国科学院地球化学研究所 Water pollutant adsorbing material and preparation method therefor
CN113198426A (en) * 2021-04-22 2021-08-03 孝感市光源电力集团有限责任公司 Chitosan resin production system and production method
CN114588883A (en) * 2020-12-07 2022-06-07 中国科学院城市环境研究所 Amine functionalized polymer material and preparation method and application thereof

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CN104059167A (en) * 2013-03-20 2014-09-24 青岛科技大学 Preparation method of polyamine compound-modified magnetic chitosan and application thereof

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CN104059167A (en) * 2013-03-20 2014-09-24 青岛科技大学 Preparation method of polyamine compound-modified magnetic chitosan and application thereof

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107804905A (en) * 2017-10-27 2018-03-16 广州安达净水材料有限公司 A kind of organic coagulants and preparation method thereof
WO2020199738A1 (en) * 2019-04-04 2020-10-08 中国科学院地球化学研究所 Water pollutant adsorbing material and preparation method therefor
CN114588883A (en) * 2020-12-07 2022-06-07 中国科学院城市环境研究所 Amine functionalized polymer material and preparation method and application thereof
CN113198426A (en) * 2021-04-22 2021-08-03 孝感市光源电力集团有限责任公司 Chitosan resin production system and production method

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