CN106823831A - A kind of preparation method and application of organic catalysis film - Google Patents

A kind of preparation method and application of organic catalysis film Download PDF

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Publication number
CN106823831A
CN106823831A CN201710126500.3A CN201710126500A CN106823831A CN 106823831 A CN106823831 A CN 106823831A CN 201710126500 A CN201710126500 A CN 201710126500A CN 106823831 A CN106823831 A CN 106823831A
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China
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kind
organic catalysis
step
preparation method
organic
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CN201710126500.3A
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Chinese (zh)
Inventor
马军
孙志强
王盼盼
刘晴靓
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哈尔滨工业大学
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Priority to CN201710126500.3A priority Critical patent/CN106823831A/en
Publication of CN106823831A publication Critical patent/CN106823831A/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D61/00Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis, ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/14Ultrafiltration; Microfiltration
    • B01D61/145Ultrafiltration
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D67/00Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D67/00Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002Organic membrane formation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D69/00Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D71/00Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06Organic material
    • B01D71/30Polyalkenyl halides
    • B01D71/32Polyalkenyl halides containing fluorine atoms
    • B01D71/34Polyvinylidene fluoride
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D71/00Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06Organic material
    • B01D71/66Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68Polysulfones; Polyethersulfones
    • 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
    • C02F1/44Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/444Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
    • 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

Abstract

A kind of preparation method and application of organic catalysis film.Field is administered the invention belongs to drink water purifying and contaminated wastewater, and in particular to a kind of preparation method and application of organic catalysis film.It is poor the invention aims to solve the problems, such as existing milipore filter removal Recalcitrant chemicals effect.Method:First, immersion fluid is prepared;2nd, organic catalysis film is prepared.Using:With a kind of organic catalysis Membrane catalysis persulfate in water treatment procedure.Preparation method of the invention directly loads the high molecular polymer with catalysis on organic film surface, prepare a kind of organic catalysis film, preparation process is simple, product is stable, the catalysis of film can be assigned while film surface hydrophilicity is improved, the antifouling property of membrane for water treatment can not only be improved, the range of application of membrane for water treatment has been widened simultaneously, with wide market prospects.

Description

A kind of preparation method and application of organic catalysis film

Technical field

Field is administered the invention belongs to drink water purifying and contaminated wastewater, and in particular to a kind of preparation side of organic catalysis film Method and application.

Background technology

Ultra filtration membrane in water treatment procedure due to treatment effeciency it is high, technological process is short, it is easy to control, use spirit Living, UF membrane water factory floor space is few, the features such as produce practicable automation, can obtain conventional conventional processes and never reach Clean water quality arrive, reliable and stable, therefore, the research and application of Ultra filtration membrane are increasingly becoming the heat of feedwater and field of sewage Point, it is referred to as obtaining one of important technology of drink water now.

But due to global science and technology and the fast development of industrial and agricultural production, water pollutant gradually become variation, complicate, Difficult removalization, such as agricultural chemicals, POPs, the appearance of antibiotic water pollution problems so as to sieve and retain surpassing for main purpose Filter film technology can not meet current water process requirement, therefore, the multifunctionality for strengthening current membrane material seems particularly critical.

Catalytic oxidation technologies Recalcitrant chemicals in water is processed are proved that extremely effectively water oxygen agent is in catalyst The lower ROS for producing of effect with persistent organic pollutants in the efficient oxidation decomposition water due to superpower oxidability, can be reached To preferable removal effect.

The content of the invention

It is poor the invention aims to solve the problems, such as existing milipore filter removal Recalcitrant chemicals effect, and provide a kind of The preparation method and application of organic catalysis film.

A kind of preparation method of organic catalysis film of the invention is carried out according to the following steps:

First, immersion fluid is prepared:To high molecular polymer is added in cushioning liquid, macromolecule polymer solution is obtained;

High molecular polymer described in step one is the polymer with phenol-quinone functional group;

Cushioning liquid described in step one is the aqueous solution or biphosphate of three (methylol) aminomethane-hydrogen chloride The aqueous solution of sodium-disodium-hydrogen;

The concentration of high molecular polymer is 1g/L~4g/L in macromolecule polymer solution described in step one;

Buffered in the amount of the material of high molecular polymer and cushioning liquid in macromolecule polymer solution described in step one The ratio of the amount of the material of thing is 1:1~2;

2nd, organic catalysis film is prepared:Membrane for water treatment is immersed in the macromolecule polymer solution obtained in step one, so After be placed in shaking bath, temperature be 20~30 DEG C and rotating speed be 30r/min~80r/min at the uniform velocity under the conditions of react 6h~ 15h, takes out, and with deionized water rinsing 5~10 times, obtains organic catalysis film.

A kind of application of organic catalysis film of the invention is with a kind of organic catalysis Membrane catalysis over cure in water treatment procedure Hydrochlorate.

Beneficial effects of the present invention:

Preparation method of the invention directly loads the high molecular polymer with catalysis on organic film surface, prepares A kind of organic catalysis film, specific advantage is as follows:

(1) preparation process of the present invention is simple, product stabilization

(2) catalysis of film can be assigned while film surface hydrophilicity is improved, membrane for water treatment can be not only improved Antifouling property, while the range of application of membrane for water treatment has been widened, with wide market prospects.

Brief description of the drawings

Fig. 1 is to test treatment effect figure of the organic catalysis film to antibiotic SMZ in two.

Specific embodiment

Specific embodiment one:A kind of preparation method of organic catalysis film of present embodiment is carried out according to the following steps:

First, immersion fluid is prepared:To high molecular polymer is added in cushioning liquid, macromolecule polymer solution is obtained;

High molecular polymer described in step one is the polymer with phenol-quinone functional group;

Cushioning liquid described in step one is the aqueous solution or biphosphate of three (methylol) aminomethane-hydrogen chloride The aqueous solution of sodium-disodium-hydrogen;

The concentration of high molecular polymer is 1g/L~4g/L in macromolecule polymer solution described in step one;

Buffered in the amount of the material of high molecular polymer and cushioning liquid in macromolecule polymer solution described in step one The ratio of the amount of the material of thing is 1:1~2;

2nd, organic catalysis film is prepared:Membrane for water treatment is immersed in the macromolecule polymer solution obtained in step one, so After be placed in shaking bath, temperature be 20~30 DEG C and rotating speed be 30r/min~80r/min at the uniform velocity under the conditions of react 6h~ 15h, takes out, and with deionized water rinsing 5~10 times, obtains organic catalysis film.

Macromolecule polymer solution described in step one is that the high molecular polymer with cushioning liquid as buffer system is molten Liquid.

The preparation method of present embodiment directly loads the high molecular polymer with catalysis, system on organic film surface For a kind of organic catalysis film is gone out, specific advantage is as follows:

(1) present embodiment preparation process is simple, product stabilization

(2) catalysis of film can be assigned while film surface hydrophilicity is improved, membrane for water treatment can be not only improved Antifouling property, while the range of application of membrane for water treatment has been widened, with wide market prospects.

Specific embodiment two:Present embodiment from unlike specific embodiment one:Macromolecule described in step one Polymer is poly-dopamine or melanin.Other steps and parameter are identical with specific embodiment one.

Specific embodiment three:Present embodiment from unlike specific embodiment one or two:Delay described in step one It is 7.5~8.5 to rush solution ph.Other steps and parameter are identical with specific embodiment one or two.

Specific embodiment four:Unlike one of present embodiment and specific embodiment one to three:Institute in step one State the ratio of the amount of the material of three (methylol) aminomethanes and hydrogen chloride in the aqueous solution of three (methylol) aminomethane-hydrogen chloride It is 1:1~3.Other steps and parameter are identical with one of specific embodiment one to three.

Specific embodiment five:Unlike one of present embodiment and specific embodiment one to four:Institute in step one The amount ratio for stating the material of sodium dihydrogen phosphate and disodium-hydrogen in the aqueous solution of sodium dihydrogen phosphate-disodium-hydrogen is 1:1.5~ 39.Other steps and parameter are identical with one of specific embodiment one to four.

Specific embodiment six:Unlike one of present embodiment and specific embodiment one to five:Institute in step one The concentration for stating high molecular polymer in macromolecule polymer solution is 2g/L.Other steps and parameter and specific embodiment one to One of five is identical.

Specific embodiment seven:Unlike one of present embodiment and specific embodiment one to six:Institute in step 2 Membrane for water treatment is stated for Kynoar (PVDF) milipore filter, polyether sulfone (PES) milipore filter or polysulfones (PSF) milipore filter.Other steps Rapid and parameter is identical with one of specific embodiment one to six.

Specific embodiment eight:Unlike one of present embodiment and specific embodiment one to seven:In step 2 Temperature be 25 DEG C and rotating speed be 50r/min at the uniform velocity under the conditions of react 12h.Other steps and parameter and specific embodiment one to seven One of it is identical.

Specific embodiment nine:A kind of application of organic catalysis film of present embodiment is with one kind in water treatment procedure Organic catalysis Membrane catalysis persulfate.

Specific embodiment ten:Present embodiment from unlike specific embodiment nine:The persulfate was one Potassium sulfate, permonosulphuric acid sodium, ammonium persulfate, potassium peroxydisulfate and one or more combination in sodium peroxydisulfate.Other steps and parameter It is identical with specific embodiment nine.

Effect of the invention is verified with following experiment

A kind of experiment one, preparation method of organic catalysis film of this experiment is carried out according to the following steps:

First, immersion fluid is prepared:To high molecular polymer is added in cushioning liquid, macromolecule polymer solution is obtained;

High molecular polymer described in step one is Dopamine hydrochloride;

Cushioning liquid described in step one is the aqueous solution of three (methylol) aminomethane-hydrogen chloride;

Wherein pH value of buffer solution is 8.5;

Wherein three (methylol) aminomethanes are 1 with the ratio of the amount of the material of hydrogen chloride:2.

The concentration of high molecular polymer is 2g/L in macromolecule polymer solution described in step one;

Three (hydroxyls in the amount of the material of high molecular polymer and cushioning liquid in macromolecule polymer solution described in step one Methyl) ratio of amount sum of material of aminomethane and hydrogen chloride is 1:1;

2nd, organic catalysis film is prepared:Membrane for water treatment is immersed in the macromolecule polymer solution obtained in step one, so After be placed in shaking bath, temperature be 25 DEG C and rotating speed be 50r/min at the uniform velocity under the conditions of react 12h, take out, use deionized water Rinse 5 times, obtain organic catalysis film;

Membrane for water treatment described in step 2 is polyvinylidene fluoride (PVDF) ultrafiltration membrane.

Experiment two, experiment one as described in a kind of organic catalysis film application:With the preparation of experiment one in water treatment procedure A kind of organic catalysis Membrane catalysis persulfate, realizes the removal to antibiotic sulfamethoxazole (SMZ) in water.

The persulfate is ammonium persulfate.

Result is shown in Fig. 1, and prepared organic catalysis Membrane catalysis persulfate is to plain sulfamethoxazole in water as can be seen from Figure 1 (SMZ) there is preferable removal effect, clearance reaches more than 80%.

Claims (10)

1. a kind of preparation method of organic catalysis film, it is characterised in that a kind of preparation method of organic catalysis film is entered according to the following steps OK:
First, immersion fluid is prepared:To high molecular polymer is added in cushioning liquid, macromolecule polymer solution is obtained;
High molecular polymer described in step one is the polymer with phenol-quinone functional group;
Cushioning liquid described in step one is the aqueous solution or sodium dihydrogen phosphate-phosphorus of three (methylol) aminomethane-hydrogen chloride The aqueous solution of a sour hydrogen sodium;
The concentration of high molecular polymer is 1g/L~4g/L in macromolecule polymer solution described in step one;
Cushion in the amount of the material of high molecular polymer and cushioning liquid in macromolecule polymer solution described in step one The ratio of the amount of material is 1:1~2;
2nd, organic catalysis film is prepared:Membrane for water treatment is immersed in the macromolecule polymer solution obtained in step one, is then put In shaking bath, temperature be 20~30 DEG C and rotating speed be 30r/min~80r/min at the uniform velocity under the conditions of react 6h~15h, take Go out, with deionized water rinsing 5~10 times, obtain organic catalysis film.
2. a kind of preparation method of organic catalysis film according to claim 1, it is characterised in that high score described in step one Sub- polymer is poly-dopamine or melanin.
3. the preparation method of a kind of organic catalysis film according to claim 1, it is characterised in that buffered described in step one Solution ph is 7.5~8.5.
4. a kind of preparation method of organic catalysis film according to claim 1, it is characterised in that three (hydroxyl described in step one Methyl) aminomethane-hydrogen chloride the aqueous solution in the ratio of amount of material of three (methylol) aminomethanes and hydrogen chloride be 1:1~ 3。
5. a kind of preparation method of organic catalysis film according to claim 1, it is characterised in that phosphoric acid described in step one Sodium dihydrogen phosphate and the amount ratio of the material of disodium-hydrogen are 1 in the aqueous solution of sodium dihydrogen-disodium-hydrogen:1.5~39.
6. a kind of preparation method of organic catalysis film according to claim 1, it is characterised in that high score described in step one The concentration of high molecular polymer is 2g/L in sub- polymer solution.
7. the preparation method of a kind of organic catalysis film according to claim 1, it is characterised in that described in step 2 at water Reason film is polyvinylidene fluoride (PVDF) ultrafiltration membrane, poly (ether-sulfone) ultrafiltration membrane or polysulphone super-filter membrane.
8. the preparation method of a kind of organic catalysis film according to claim 1, it is characterised in that be in temperature in step 2 25 DEG C and rotating speed be 50r/min at the uniform velocity under the conditions of react 12h.
9. a kind of application of organic catalysis film, it is characterised in that with a kind of organic catalysis Membrane catalysis persulfuric acid in water treatment procedure Salt.
10. a kind of application of organic catalysis film, it is characterised in that the persulfate is permonosulphuric acid potassium, permonosulphuric acid sodium, mistake Ammonium sulfate, potassium peroxydisulfate and one or more combination in sodium peroxydisulfate.
CN201710126500.3A 2017-03-03 2017-03-03 A kind of preparation method and application of organic catalysis film CN106823831A (en)

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US20150274892A1 (en) * 2014-03-25 2015-10-01 Northwestern University Dopa-melanin formation in high ionic strength solutions
CN105169970A (en) * 2015-09-08 2015-12-23 武汉大学 Preparation method for polydopamine-modified polyamide composite forward osmosis membrane
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Application publication date: 20170613