CN108636452A - A kind of preparation method and applications of chitosan loaded Zero-valent Iron pellet catalyst - Google Patents

A kind of preparation method and applications of chitosan loaded Zero-valent Iron pellet catalyst Download PDF

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Publication number
CN108636452A
CN108636452A CN201810470825.8A CN201810470825A CN108636452A CN 108636452 A CN108636452 A CN 108636452A CN 201810470825 A CN201810470825 A CN 201810470825A CN 108636452 A CN108636452 A CN 108636452A
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China
Prior art keywords
valent iron
chitosan
zero
added
chitosan loaded
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CN201810470825.8A
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Chinese (zh)
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CN108636452B (en
Inventor
洪俊明
董正玉
张倩
王炳煌
吴丽颖
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Huaqiao University
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Huaqiao University
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Priority claimed from CN201810470825.8A external-priority patent/CN108636452B/en
Publication of CN108636452A publication Critical patent/CN108636452A/en
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Publication of CN108636452B publication Critical patent/CN108636452B/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/02Solids
    • B01J35/08Spheres
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/722Oxidation by peroxides
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/725Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00Use of specific compounds during water treatment
    • C02F2305/02Specific form of oxidant

Abstract

The invention discloses a kind of preparation method and applications of chitosan loaded Zero-valent Iron pellet catalyst, include the following steps:(1) chitosan and FeCl3·6H2O is added in deionized water, stirring and dissolving, obtains mixed gel;(2) zeroth order iron powder is added into mixed gel solution, obtains mixed liquor;(3) mixed liquor is added dropwise with syringe in NaOH solution and forms chitosan loaded Zero-valent Iron bead;(4) chitosan loaded Zero-valent Iron bead ethyl alcohol and deionized water prepared by step (3) are washed till supernatant and is in neutrality, be dried in vacuo.Chitosan loaded Zero-valent Iron pellet catalyst prepared by the present invention acts synergistically with persulfate, without external energy, condition needed for reaction can be reached under room temperature condition of neutral pH, compared to homogeneous persulfate system, heterogeneous persulfate system can continuously provide potentiometric titrations and reduce the burst size of metal ion, to which the organic pollution in sustaining degradation water also prevents secondary pollution.

Description

A kind of preparation method and applications of chitosan loaded Zero-valent Iron pellet catalyst
Technical field
The invention belongs to catalyst technical fields, and in particular to a kind of preparation of chitosan loaded Zero-valent Iron pellet catalyst Method and its application.
Background technology
Advanced oxidation processes have been widely studied, and can be used for removing the organic matter of bio-refractory.Fenton and Fenton-like Reaction the advantage is that the hydroxyl radical free radical with strong oxidizing property of generation as more one kind is applied in chemical oxidization method, It being capable of the effectively most of organic matter of oxidative degradation.But (pH value is 3.0 left since it is more harsh to reaction condition requirement It is right), H2O2It is expensive, preserve difficult, subsequent biochemical processing needs to carry out pH adjustings to water inlet, so as to cause processing cost It is excessively high.
Based on potentiometric titrations (SO4 -) persulfate (PS) and peroxy-monosulfate (PMS) high-level oxidation technology It is a kind of advanced oxidation technology developed in recent years.Since its reaction condition is mild, pH value is not depended on, is generated The very strong oxidisability of potentiometric titrations and half-life period is longer than hydroxyl radical free radical, can continued oxidation organic matter until its mine Change.Transition metal ions (such as Fe2+, Cu2+, Ag+And Co2+) have been demonstrated effectively activate PS.In particular, Fe2+Often It is used to treat.It is similar with Fenton systems with degradation of contaminant that Zero-valent Iron and nano zero valence iron can more effectively activate PS, However Fe0High Fe in/PS systems2+Concentration can lead to SO4 -Removing, therefore the degradation efficiency of pollutant can be reduced.Release Iron ion and iron sludge concentration is excessively high can cause environmental pollution certainly.In addition, ferrous ion is easily oxidized into ferric iron, Catalytic activity is caused to reduce.Consider long-term disposal, carrier matrix appropriate can be used rather than pure Fe0Or Dissolvable Fe2+Come Improve the sustainable usability of catalyst.Therefore, iron substance is loaded on solid matrix materials and seems to be hopeful to be formed to have The heterogeneous catalysis of suitable validity.
Chitosan (CS) is the deacetylated linear natural polysaccharide obtained of all or part from chitin.In recent years, by Cheap and easy to get in chitosan, the ability of environment friendly and excellent bond wire ion makes its load as ferrite based substances Object is widely studied use.
Currently, have research that chitosan loaded crosslinking metal ions is used to be reacted for Fenton as catalyst, but in mistake It is also studied on the catalytic effect of sulfate not yet ripe.
Invention content
It is an object of the invention to overcome prior art defect, a kind of chitosan loaded Zero-valent Iron pellet catalyst is provided Preparation method.
Another object of the present invention is to provide the applications of above-mentioned chitosan loaded Zero-valent Iron pellet catalyst.
Technical scheme is as follows:
A kind of preparation method of chitosan loaded Zero-valent Iron pellet catalyst, includes the following steps:
(1) chitosan and FeCl3·6H2O is added in deionized water, stirring and dissolving, obtains mixed gel;
(2) it is stirred evenly after zeroth order iron powder being added into the mixed gel solution obtained by step (1), obtains mixed liquor;
(3) mixed liquor obtained by step (2) is added dropwise with syringe in NaOH solution and forms chitosan loaded zeroth order Iron bead;
(4) chitosan loaded Zero-valent Iron bead ethyl alcohol and deionized water prepared by step (3) are washed till during supernatant is in Property, 12~16h is dried in vacuo at 60~65 DEG C to get the chitosan loaded Zero-valent Iron pellet catalyst.
In a preferred embodiment of the invention, in the step (1), chitosan and FeCl3·6H2The mass ratio of O It is 1: 2~3.
In a preferred embodiment of the invention, the step (2) is:It is molten to the mixed gel obtained by step (1) It is stirred evenly after zeroth order iron powder to final concentration of 0.04~0.07mol/L is added in liquid, obtains mixed liquor.
In a preferred embodiment of the invention, a concentration of 1.0 of the sodium hydroxide solution in the step (3)~ 3.0mol/L。
Chitosan loaded Zero-valent Iron pellet catalyst prepared by above-mentioned preparation method is useless containing organic pollution in processing Application in water.
In a preferred embodiment of the invention, including:Under conditions of room temperature and neutral pH, by the chitosan It is added in the waste water together with load Zero-valent Iron pellet catalyst and persulfate, concentration of the persulfate in the waste water For 1.0~3.0mM, a concentration of 0.8~1.2g/L of the chitosan loaded Zero-valent Iron pellet catalyst in the waste water.
It is further preferred that the persulfate is sodium peroxydisulfate and/or potassium peroxydisulfate.
The beneficial effects of the invention are as follows:
1, chitosan loaded Zero-valent Iron pellet catalyst prepared by preparation method of the invention is added together with persulfate In waste water containing organic pollution, the two contacts to form a large amount of potentiometric titrations with strong oxidizing property, to which oxidation has Machine pollutant makes its degradation,
2, the chitosan loaded Zero-valent Iron pellet catalyst and persulfate that prepared by the present invention act synergistically, and are not necessarily to additional energy It measures, condition needed for reaction can be reached under room temperature condition of neutral pH, compared to homogeneous persulfate system, heterogeneous persulfate System can continuously provide potentiometric titrations and reduce the burst size of metal ion, in sustaining degradation water Organic pollution also prevents secondary pollution.
3, the more simple Zero-valent Iron of the chitosan loaded Zero-valent Iron pellet catalyst of preparation method of the invention preparation can More there is more effectively control metal ion to leach.
Description of the drawings
Fig. 1 is that the electron microscope of the finally obtained chitosan loaded Zero-valent Iron pellet catalyst of the embodiment of the present invention 1 shines Piece.
Fig. 2 be the embodiment of the present invention 1 prepare chitosan loaded Zero-valent Iron pellet catalyst pictorial diagram (Fig. 2 (a) be baking Before dry;Fig. 2 (b) is after drying).
Fig. 3 is that different systems handle the design sketch of paracetamol and metal ion leaching in water in the embodiment of the present invention 1.
Specific implementation mode
Technical scheme of the present invention is further detailed and is described below by way of specific implementation mode combination attached drawing.
Embodiment 1
(1) chitosan and FeCl3·6H2O be added deionized water in, stirring and dissolving, obtain mixed gel, chitosan and FeCl3·6H2The mass ratio of O is 1: 2~3;
(2) zeroth order iron powder is added into the mixed gel solution obtained by step (1) to final concentration of 0.04~0.07mol/L After stir evenly, obtain mixed liquor;
(3) mixed liquor obtained by step (2) is added dropwise to the NaOH solution of a concentration of 1.0~3.0mol/L with syringe It is middle to form chitosan loaded Zero-valent Iron bead (as shown in Figure 2);
(4) chitosan loaded Zero-valent Iron bead ethyl alcohol and deionized water prepared by step (3) are washed till during supernatant is in Property, 12~16h is dried in vacuo at 60~65 DEG C to get chitosan loaded Zero-valent Iron pellet catalyst as illustrated in fig. 1 and 2
The paracetamol solution that 100mL contains 30mg/L is added into reactor, sodium peroxydisulfate and shell are added into solution Glycan loads Zero-valent Iron pellet catalyst, and it is respectively 3.0mM and 1.2g/L to make its concentration.It is handled and is imitated with high performance liquid chromatography detection Fruit, as shown in figure 3, in the case where room temperature and pH value are neutrallty condition.Degradation efficiency after paracetamol 35min is 98.5%, total iron Leaching content is 11.3mg/L.
Comparative example 1
Using same system, the paracetamol solution that 100mL contains 30mg/L is added into reactor, is added into solution Sodium peroxydisulfate, it is respectively 3.0mM to make its concentration, and individual zeroth order iron powder is added.With high performance liquid chromatography detection treatment effect, such as Shown in Fig. 3, in the case where room temperature and pH value are neutrallty condition, total iron leaching content is 32.3mg/L, the catalysis prepared much larger than the present invention Agent.
The foregoing is only a preferred embodiment of the present invention, therefore cannot limit the scope of implementation of the present invention according to this, i.e., According to equivalent changes and modifications made by the scope of the claims of the present invention and description, all should still belong in the range of the present invention covers.

Claims (7)

1. a kind of preparation method of chitosan loaded Zero-valent Iron pellet catalyst, it is characterised in that:Include the following steps:
(1) chitosan and FeCl3·6H2O is added in deionized water, stirring and dissolving, obtains mixed gel;
(2) it is stirred evenly after zeroth order iron powder being added into the mixed gel solution obtained by step (1), obtains mixed liquor;
(3) mixed liquor obtained by step (2) is added dropwise with syringe in NaOH solution to form chitosan loaded Zero-valent Iron small Ball;
(4) chitosan loaded Zero-valent Iron bead ethyl alcohol and deionized water prepared by step (3) are washed till supernatant and is in neutrality, 12~16h is dried in vacuo at 60~65 DEG C to get the chitosan loaded Zero-valent Iron pellet catalyst.
2. preparation method as described in claim 1, it is characterised in that:In the step (1), chitosan and FeCl3·6H2O's Mass ratio is 1: 2~3.
3. preparation method as described in claim 1, it is characterised in that:The step (2) is:To the mixing obtained by step (1) It is stirred evenly after zeroth order iron powder to final concentration of 0.04~0.07mol/L is added in gel solution, obtains mixed liquor.
4. preparation method as described in claim 1, it is characterised in that:The concentration of sodium hydroxide solution in the step (3) For 1.0~3.0mol/L.
5. chitosan loaded Zero-valent Iron bead catalysis prepared by the preparation method in Claims 1-4 described in any claim Application of the agent in handling the waste water containing organic pollution.
6. application as claimed in claim 5, it is characterised in that:Including:Under conditions of room temperature and neutral pH, the shell is gathered It is added in the waste water together with sugar load Zero-valent Iron pellet catalyst and persulfate, persulfate is dense in the waste water Degree is 1.0~3.0mM, a concentration of 0.8~1.2g/L of the chitosan loaded Zero-valent Iron pellet catalyst in the waste water.
7. application as claimed in claim 6, it is characterised in that:The persulfate is sodium peroxydisulfate and/or potassium peroxydisulfate.
CN201810470825.8A 2018-05-16 Preparation method and application of chitosan loaded zero-valent iron pellet catalyst CN108636452B (en)

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Application Number Priority Date Filing Date Title
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Application Number Priority Date Filing Date Title
CN201810470825.8A CN108636452B (en) 2018-05-16 Preparation method and application of chitosan loaded zero-valent iron pellet catalyst

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CN108636452A true CN108636452A (en) 2018-10-12
CN108636452B CN108636452B (en) 2021-04-30

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103480341A (en) * 2013-10-14 2014-01-01 中国科学院城市环境研究所 Hydrogel material capable of removing arsenic
CN105110448A (en) * 2015-10-09 2015-12-02 中国科学院南海海洋研究所 Method for removing heavy metal and organic matter composite pollutants in water body by means of zero-valent iron and persulfate
CN105646902A (en) * 2016-04-01 2016-06-08 江苏大学 Preparation method of iron-chitosan metal supermolecular gel
CN107445289A (en) * 2017-08-22 2017-12-08 西安交通大学 PVA/ chitosan sphere bio-carriers and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103480341A (en) * 2013-10-14 2014-01-01 中国科学院城市环境研究所 Hydrogel material capable of removing arsenic
CN105110448A (en) * 2015-10-09 2015-12-02 中国科学院南海海洋研究所 Method for removing heavy metal and organic matter composite pollutants in water body by means of zero-valent iron and persulfate
CN105646902A (en) * 2016-04-01 2016-06-08 江苏大学 Preparation method of iron-chitosan metal supermolecular gel
CN107445289A (en) * 2017-08-22 2017-12-08 西安交通大学 PVA/ chitosan sphere bio-carriers and preparation method thereof

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