CN105399197A - Method for processing dye waste water based on activation of peroxymonosufate by three-dimensional ordered mesoporous CoFe2O4 - Google Patents

Method for processing dye waste water based on activation of peroxymonosufate by three-dimensional ordered mesoporous CoFe2O4 Download PDF

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CN105399197A
CN105399197A CN201510928060.4A CN201510928060A CN105399197A CN 105399197 A CN105399197 A CN 105399197A CN 201510928060 A CN201510928060 A CN 201510928060A CN 105399197 A CN105399197 A CN 105399197A
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China
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cofe
tom
persulphate
waste water
rhodamine
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CN201510928060.4A
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Chinese (zh)
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CN105399197B (en
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邓靖
冯善方
马晓雁
倪永炯
卢遇安
程永清
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浙江工业大学
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    • 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02Sulfur, selenium or tellurium; Compounds thereof
    • 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
    • B01J35/10Solids characterised by their surface properties or porosity
    • B01J35/1004Surface area
    • 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
    • C02F1/48Treatment of water, waste water, or sewage with magnetic or electric fields
    • C02F1/488Treatment of water, waste water, or sewage with magnetic or electric fields for separation of magnetic materials, e.g. magnetic flocculation
    • 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
    • C02F2101/308Dyes; Colorants; Fluorescent agents

Abstract

The invention discloses a method for processing dye waste water based on activation of peroxymonosufate by three-dimensional ordered mesoporous CoFe2O4 and aims to solve the problem of low catalysis efficiency of present spinel CoFe2O4 to peroxymonosufate. The method is implemented through the following steps: firstly, three-dimensional ordered mesoporous CoFe2O4 is prepared; secondly, dye waste water with an appointed concentration is prepared, and the prepared solution is placed in a brown shake flask; thirdly, peroxymonosufate is added; fourthly, the three-dimensional ordered mesoporous CoFe2O4 is added; fifthly, the three-dimensional ordered mesoporous CoFe2O4 is separated by utilization of an applied magnetic field, and processing of dye in waste water based on activation of peroxymonosufate by three-dimensional ordered mesoporous CoFe2O4 can be completed. High-efficiency processing of dye waste water can be achieved by utilization of three-dimensional ordered mesoporous CoFe2O4 in cooperation with the peroxymonosufate technology, and the removal rate exceeds 90%. The cobalt ion leaching rate is low during the usage process, and environment pollution is reduced. The catalyst can be separated rapidly through an applied magnetic field and can be recycled, and the operation cost is lowered.

Description

Based on the method for three-dimensional magnetic order mesoporous cobalt ferrite activation persulphate dye wastewater treatment

Technical field

The present invention relates to water treatment field, disclose a kind of method based on three-dimensional magnetic order mesoporous cobalt ferrite activation persulphate dye wastewater treatment.

Background technology

The waste water from dyestuff that different industries (weaving, papermaking, leather, food, dyestuff manufacture etc.) is discharged is considered to the important sources of water pollution.According to statistics, the ultimate production about 1,000,000 ton of the annual dyestuff in the whole world.Waste water from dyestuff has the features such as colourity is large, salinity is high, biodegradability is poor, can cause great harm if be directly discharged in water body to the mankind and environment.Rhodamine B is a kind of important water-soluble xanthene organic dye, over half all containing this material in the waste water of textile industry discharge.The existence of rhodamine B can weaken the light transmission of water body, reduces the dissolved oxygen amount in water, suppresses hydrobiological photosynthesis, directly endangers hydrobiological growth and existence.What is more important, rhodamine B is a kind of suspicious carcinogenic substance, and complicated structure and stable character make it have suitable resistant function to biological treatment and photodegradation, enter in water source and may cause serious harm to mankind's safe drinking water.Therefore, need badly and seek the pollution problem that effective source and course control method for use solve rhodamine B in water surrounding.

In recent years, high-level oxidation technology is widely used in water treatment, wherein based on potentiometric titrations (SO 4 -) high-level oxidation technology be subject to extensive concern.The reaction of transition metal ion activation persulphate (Peroxymonosufate, PMS) at room temperature can be carried out fast, without the need to external energy (thermal source and light source), has broad application prospects.But there is catalyst recovery difficulty and easily cause the problems such as secondary environment pollution in homogeneous phase persulphate catalyst system.And the spinel-type cobalt of at present extensively research is less due to specific surface area, and be easy to reunite in water, greatly have impact on its catalytic efficiency to PMS.For above problem, intend preparing the order mesoporous cobalt ferrite of three-dimensional magnetic by simple, economic method, while the constitutional features utilizing its uniqueness and interfacial characteristics efficient catalytic PMS, realized the sharp separation of catalyzer by externally-applied magnetic field.Use method of the present invention can reach more than 90% to the clearance of difficult degradation organic dye in water.

Summary of the invention

The present invention is intended to solve catalyst recovery difficulty in homogeneous phase persulphate catalyst system and easily causes the secondary pollution of environment and the lower problem of spinel-type cobalt catalytic performance, proposes a kind of method based on three-dimensional magnetic order mesoporous cobalt ferrite activation persulphate degradation of dye waste water.

The technical solution adopted for the present invention to solve the technical problems is:

Based on the method for three-dimensional magnetic order mesoporous cobalt ferrite activation persulphate dye wastewater treatment, carry out according to the following steps:

One, the order mesoporous cobalt ferrite (Three-dimensionalorderedmesoporousCoFe of three-dimensional magnetic is prepared 2o 4, TOM-CoFe 2o 4);

by KIT-6 template, Co (NO 3) 26H 2o, Fe (NO 3) 39H 2o is put into successively in the mortar containing normal hexane and fully grinds, by the material transfer of fully grinding in the round-bottomed flask filling normal hexane, and return stirring 12h under 70 DEG C of water bath condition;

Step one described in KIT-6 template, Co (NO 3) 26H 2o, Fe (NO 3) 39H 2the mol ratio of O is 8:1:2;

Step one described in KIT-6 template, Co (NO 3) 26H 2o, Fe (NO 3) 39H 2o is put into successively in the mortar containing normal hexane and fully grinds, and the volume requirement of normal hexane above material can be flooded completely;

Step one described in by the material transfer of fully grinding in the round-bottomed flask filling normal hexane, return stirring 12h under 70 DEG C of water bath condition, the volume requirement of normal hexane above material can be flooded completely;

stirred solution is transferred in beaker, obtains pink solid at 70-80 DEG C of drying with water bath, by this solid transfer in crucible, and to place it in retort furnace roast 5-5.5h under 600-650 DEG C of condition;

Step one described in pink solid is moved in crucible, and to place it in retort furnace roast 5-5.5h under 600-650 DEG C of condition, the heat-up rate of retort furnace is 1-1.2 DEG C/min;

dark brown solid after roast is cooled to room temperature, and be transferred in the round-bottomed flask filling 2MNaOH solution after grinding evenly, under 70 DEG C of water bath condition, return stirring 24h is centrifugal after removing template, and above return stirring and centrifugation step repeat once;

Step one described in dark brown solid and the mass ratio of 2MNaOH solution be 1:(100 ~ 200);

Step one described in centrifugal used centrifuge speed be 8000r/min ~ 19000r/min;

after material after centrifugal uses deionized water and washing with alcohol to pH=7 respectively, 70-75 DEG C of vacuum-drying obtains dark brown solid, stores for future use after fully being ground by this solid;

Two, prepare the waste water from dyestuff of prescribed concentration, the solution prepared is installed in brown shaking flask: select typical dye rhodamine B to be target contaminant, the solution prepared is installed in brown shaking flask;

The concentration of the rhodamine B described in step 2 is 1mg/L ~ 200mg/L;

Install in brown shaking flask by the solution prepared described in step 2, in brown shaking flask, the volume of solution is 100mL ~ 200mL;

Three, persulphate is added: take persulphate by the mol ratio that rhodamine B and persulphate are certain and be added in the brown shaking flask of step 2 and mix;

Persulphate described in step 3 is a kind of or wherein several mixture in Potassium peroxysulfate, single ammonium persulphate, single Sodium Persulfate and single persulfuric acid calcium;

In persulphate described in step 3 and pretreated waste water, the mol ratio of rhodamine B is (1 ~ 50): 1;

Four, TOM-CoFe is added 2o 4: by TOM-CoFe 2o 4be added in step 3 and fully stir containing in the brown shaking flask of mixing solutions, keep reacting liquid temperature to be 20 ~ 50 DEG C and react 30min ~ 120min with pH under the condition of 3 ~ 9, the efficient removal of rhodamine B in waste water can be realized, and obtain containing TOM-CoFe 2o 4solution;

TOM-CoFe described in step 4 2o 4dosage be 10mg/L ~ 500mg/L;

Five, externally-applied magnetic field is adopted to be separated TOM-CoFe 2o 4: adopt externally-applied magnetic field to be separated TOM-CoFe 2o 4, the TOM-CoFe of recovery 2o 4carry out washing with ethanol and deionized water and 70 DEG C of vacuum-dryings, the TOM-CoFe be recycled 2o 4.

The mechanism of this patent is that homogeneous phase persulphate system exists catalyst recovery difficulty and easily causes the problem of secondary environmental pollution; And current spinel type CoFe 2o 4specific surface area is little (is usually less than 10m 2/ g), and be easy in the solution reunite, seriously reduce its catalytic capability to persulphate.And the TOM-CoFe of employing of the present invention 2o 4possess huge specific surface area and abundant pore texture, spinel type CoFe can be solved preferably 2o 4problems existing, thus catalysis persulphate produces SO4 efficiently -degradable organic pollutant; At TOM-CoFe 2o 4use procedure in, Co 2+stripping concentration extremely low, reduce the pollution to environment; TOM-CoFe 2o 4magnetic ensure that it reclaims quickly and easily by externally-applied magnetic field after the completion of reaction; And metal ion Co 2+/ Co 3+valence transition and persulphate decompose between balance ensure that catalyzer continues efficient catalytic performance.

Beneficial effect of the present invention is as follows:

1.TOM-CoFe 2o 4tOM-CoFe in/PMS system 2o 4sO4 can be produced by efficient catalytic persulphate -, simple to operate, save energy, without the need to carrying out uv irradiation, ultrasonic cavitation, heating etc. to system;

2.TOM-CoFe 2o 4tOM-CoFe in/PMS system 2o 4possess huge specific surface area and abundant pore texture, more easily can contact with organic dye with persulphate, greatly improve catalytic efficiency;

3.TOM-CoFe 2o 4tOM-CoFe in/PMS system 2o 4sO4 can be produced by efficient catalytic persulphate -oxidative degradation organism, clearance is more than 90%;

4.TOM-CoFe 2o 4tOM-CoFe in/PMS system 2o 4there is magnetic, recycle and reuse by externally-applied magnetic field, reduce running cost.

Accompanying drawing explanation

Fig. 1 is rhodamine B concentration curve over time under different working condition.

Wherein show and add TOM-CoFe separately 2o 4rhodamine B concentration curve over time under condition; Wherein represent and add separately rhodamine B concentration curve over time under PMS condition; represent spinel type CoFe 2o 4rhodamine B concentration curve over time under the condition of collaborative PMS; represent TOM-CoFe 2o 4rhodamine B concentration curve over time under the condition of collaborative PMS.

Fig. 2 is that reuse number of times is to TOM-CoFe 2o 4the impact of collaborative PMS rhodamine B degradation.

represent reuse 0 TOM-CoFe 2o 4rhodamine B concentration curve over time under the condition of collaborative PMS; represent reuse TOM-CoFe once 2o 4rhodamine B concentration curve over time under the condition of collaborative PMS; represent the TOM-CoFe of reuse secondary 2o 4rhodamine B concentration curve over time under the condition of collaborative PMS; represent that the use of reuse three times works in coordination with rhodamine B concentration curve over time under the condition of PMS; represent that the use of reuse four times works in coordination with rhodamine B concentration curve over time under the condition of PMS.

Embodiment

Technical solution of the present invention is not limited to and exemplifies specific implementation method below, also comprises the arbitrary combination between each embodiment.

Embodiment one:

A kind of method based on three-dimensional magnetic order mesoporous cobalt ferrite activation persulphate dye wastewater treatment in present embodiment, carry out according to the following steps:

One, the order mesoporous cobalt ferrite (Three-dimensionalorderedmesoporousCoFe of three-dimensional magnetic is prepared 2o 4, TOM-CoFe 2o 4);

by KIT-6 template, Co (NO 3) 26H 2o, Fe (NO 3) 39H 2o is put into successively in the mortar containing normal hexane and fully grinds, by the material transfer of fully grinding in the round-bottomed flask filling normal hexane, and return stirring 12h under 70 DEG C of water bath condition;

Step one described in KIT-6 template, Co (NO 3) 26H 2o, Fe (NO 3) 39H 2the mol ratio of O is 8:1:2;

Step one described in KIT-6 template, Co (NO 3) 26H 2o, Fe (NO 3) 39H 2o is put into successively in the mortar containing normal hexane and fully grinds, and the volume requirement of normal hexane above material can be flooded completely;

Step one described in by the material transfer of fully grinding in the round-bottomed flask filling normal hexane, return stirring 12h under 70 DEG C of water bath condition, the volume requirement of normal hexane above material can be flooded completely;

stirred solution is transferred in beaker, obtains pink solid at 70 DEG C of drying with water baths, by this solid transfer in crucible, and to place it in retort furnace roast 5h under 600 DEG C of conditions;

Step one described in pink solid is moved in crucible, and to place it in retort furnace roast 5h under 600 DEG C of conditions, the heat-up rate of retort furnace is 1 DEG C/min;

dark brown solid after roast is cooled to room temperature, is transferred in the round-bottomed flask of 2MNaOH solution after grinding evenly, under 70 DEG C of water bath condition, return stirring 24h is centrifugal after removing template, and above return stirring and centrifugation step repeat once;

Step one described in dark brown solid and the mass ratio of 2MNaOH solution be 1:(100 ~ 200);

Step one described in centrifugal used centrifuge speed be 8000r/min ~ 19000r/min;

after material after centrifugal uses deionized water and washing with alcohol to pH=7 respectively, 70 DEG C of vacuum-dryings obtain dark brown solid, store for future use after fully being ground by this solid;

Two, prepare the waste water from dyestuff of prescribed concentration, the solution prepared is installed in brown shaking flask: select typical dye rhodamine B to be target contaminant, the solution prepared is installed in brown shaking flask.

The concentration of the rhodamine B described in step 2 is 1mg/L ~ 50mg/L;

Install in brown shaking flask by the solution prepared described in step 2, in brown shaking flask, the volume of solution is 100mL ~ 200mL;

Three, persulphate is added: take persulphate by the mol ratio that rhodamine B and persulphate are certain and be added in the brown shaking flask of step 2 and mix;

Persulphate described in step 3 is a kind of or wherein several mixture in Potassium peroxysulfate, single ammonium persulphate, single Sodium Persulfate and single persulfuric acid calcium;

In persulphate described in step 3 and pretreated waste water, the mol ratio of rhodamine B is (20 ~ 50): 1;

Four, TOM-CoFe is added 2o 4: by TOM-CoFe 2o 4be added in step 3 and fully stir containing in the brown shaking flask of mixing solutions, keep reacting liquid temperature to be react 30min ~ 120min under the condition of 20 ~ 30 DEG C and pH=3 ~ 6, the efficient removal of rhodamine B in waste water can be realized, and obtain containing TOM-CoFe 2o 4solution.

Three TOM-CoFe described in step 4 2o 4dosage be 10mg/L ~ 100mg/L;

Five, externally-applied magnetic field is adopted to be separated TOM-CoFe 2o 4: adopt externally-applied magnetic field to be separated TOM-CoFe 2o 4, the TOM-CoFe of recovery 2o 4carry out washing with ethanol and deionized water and 70 DEG C of vacuum-dryings, the TOM-CoFe be recycled 2o 4.

Embodiment two:

Present embodiment and embodiment one are 50mg/L ~ 100mg/L unlike the concentration of target contaminant rhodamine B in step 2, other steps and parameter identical with embodiment one.

Embodiment three:

Present embodiment and embodiment one to two are 100mg/L ~ 200mg/L unlike the concentration of target contaminant rhodamine B in step 2, other steps and parameter identical with one of embodiment one to two.

Embodiment four:

Present embodiment and embodiment one to three are (1 ~ 20) unlike the mol ratio of step 3 persulphate and target contaminant: 1.Other steps and parameter identical with one of embodiment one to three.

Embodiment five:

One of present embodiment and embodiment one to four are unlike TOM-CoFe in step 4 2o 4dosage be 100mg/L ~ 300mg/L.Other steps and parameter identical with one of embodiment one to four.

Embodiment six:

One of present embodiment and embodiment one to five are unlike TOM-CoFe in step 4 2o 4dosage be 300mg/L ~ 500mg/L.Other steps and parameter identical with one of embodiment one to five.

Embodiment seven:

One of present embodiment and embodiment one to six are 30 DEG C ~ 50 DEG C unlike temperature of reaction system in step 4.Other steps and parameter identical with one of embodiment one to six.

Embodiment eight:

One of present embodiment and embodiment one to seven are 6 ~ 9 unlike reaction system pH in step 4.Other steps and parameter identical with one of embodiment one to seven.

Embodiment nine:

One of present embodiment and embodiment one to eight are unlike the TOM-CoFe added in step 4 2o 4for in step 5 by TOM-CoFe that externally-applied magnetic field reclaims 2o 4.Other steps and parameter identical with one of embodiment one to eight.

In order to verify beneficial effect of the present invention, carry out following experiment:

Experiment one:

A kind of based on TOM-CoFe 2o 4/ PMS technique is carried out by the following method to the degradation experiment of rhodamine B:

One, TOM-CoFe is prepared 2o 4;

by KIT-6 template, Co (NO 3) 26H 2o, Fe (NO 3) 39H 2o is put into successively in the mortar containing normal hexane and fully grinds, by the material transfer of fully grinding in the round-bottomed flask filling normal hexane, and return stirring 12h under 70 DEG C of water bath condition;

Step one described in KIT-6 template, Co (NO 3) 26H 2o, Fe (NO 3) 39H 2the mol ratio of O is 8:1:2;

Step one described in KIT-6 template, Co (NO 3) 26H 2o, Fe (NO 3) 39H 2o is put into successively in the mortar containing normal hexane and fully grinds, and the volume requirement of normal hexane above material can be flooded completely;

Step one described in by the material transfer of fully grinding in the round-bottomed flask filling normal hexane, return stirring 12h under 70 DEG C of water bath condition, the volume requirement of normal hexane above material can be flooded completely;

stirred solution is transferred in beaker, obtains pink solid at 70 DEG C of drying with water baths, by this solid transfer in crucible, and to place it in retort furnace roast 5h under 600 DEG C of conditions;

Step one described in pink solid is moved in crucible, and to place it in retort furnace roast 5h under 600 DEG C of conditions, the heat-up rate of retort furnace is 1 DEG C/min;

dark brown solid after roast is cooled to room temperature, is transferred in the round-bottomed flask of 2MNaOH solution after grinding evenly, under 70 DEG C of water bath condition, return stirring 24h is centrifugal after removing template, and above return stirring and centrifugation step repeat once;

Step one described in dark brown solid and the mass ratio of 2MNaOH solution be 1:(100 ~ 200);

Step one described in centrifugal used centrifuge speed be 8000r/min ~ 19000r/min;

after material after centrifugal uses deionized water and washing with alcohol to pH=7 respectively, obtain dark brown solid 70 DEG C of vacuum-dryings, store for future use after this solid is fully ground;

Two, prepare the waste water from dyestuff of prescribed concentration, the solution prepared is installed in brown shaking flask: select typical dye rhodamine B to be target contaminant, the solution prepared is installed in brown shaking flask;

The concentration of the rhodamine B described in step 2 is 20mg/L;

Install in brown shaking flask by the solution prepared described in step 2, in brown shaking flask, the volume of solution is 100mL;

Three, persulphate is added: take persulphate by the mol ratio that rhodamine B and persulphate are certain and be added in the brown shaking flask of step 2 and mix;

Persulphate described in step 3 is a kind of or wherein several mixture in Potassium peroxysulfate, single ammonium persulphate, single Sodium Persulfate and single persulfuric acid calcium;

In persulphate described in step 3 and pretreated waste water, the mol ratio of rhodamine B is 10:1;

Four, TOM-CoFe is added 2o 4: by TOM-CoFe 2o 4be added in step 3 and fully stir containing in the brown shaking flask of mixing solutions, keep reacting liquid temperature to be react 30min under the condition of 25 DEG C and pH=7, the efficient removal of rhodamine B in waste water can be realized, and obtain containing TOM-CoFe 2o 4solution.

TOM-CoFe described in step 4 2o 4dosage be 100mg/L;

Five, externally-applied magnetic field is adopted to be separated TOM-CoFe 2o 4: adopt externally-applied magnetic field to be separated TOM-CoFe 2o 4, the TOM-CoFe of recovery 2o 4carry out washing with ethanol and deionized water and 70 DEG C of vacuum-dryings, the TOM-CoFe of recovery 2o 4.Then complete TOM-CoFe 2o 4/ PMS technique is to the degradation experiment of rhodamine B.

Experiment two: add TOM-CoFe separately 2o 4the experiment of absorption rhodamine B is carried out by the following method:

One, TOM-CoFe is prepared 2o 4;

by KIT-6 template, Co (NO 3) 26H 2o, Fe (NO 3) 39H 2o is put into successively in the mortar containing normal hexane and fully grinds, by the material transfer of fully grinding in the round-bottomed flask filling normal hexane, and return stirring 12h under 70 DEG C of water bath condition;

Step one described in KIT-6 template, Co (NO 3) 26H 2o, Fe (NO 3) 39H 2the mol ratio of O is 8:1:2;

Step one described in KIT-6 template, Co (NO 3) 26H 2o, Fe (NO 3) 39H 2o is put into successively in the mortar containing normal hexane and fully grinds, and the volume requirement of normal hexane above material can be flooded completely;

Step one described in by the material transfer of fully grinding in the round-bottomed flask filling normal hexane, return stirring 12h under 70 DEG C of water bath condition, the volume requirement of normal hexane above material can be flooded completely;

stirred solution is transferred in beaker, obtains pink solid at 70 DEG C of drying with water baths, by this solid transfer in crucible, and to place it in retort furnace roast 5h under 600 DEG C of conditions;

Step one described in pink solid is moved in crucible, and to place it in retort furnace roast 5h under 600 DEG C of conditions, the heat-up rate of retort furnace is 1 DEG C/min;

dark brown solid after roast is cooled to room temperature, is transferred in the round-bottomed flask of 2MNaOH solution after grinding evenly, under 70 DEG C of water bath condition, return stirring 24h is centrifugal after removing template, and above return stirring and centrifugation step repeat once;

Step one described in dark brown solid and the mass ratio of 2MNaOH solution be 1:(100 ~ 200);

Step one described in centrifugal used centrifuge speed be 8000r/min ~ 19000r/min;

after material after centrifugal uses deionized water and washing with alcohol to pH=7 respectively, obtain dark brown solid 70 DEG C of vacuum-dryings, store for future use after this solid is fully ground;

Two, prepare the waste water from dyestuff of prescribed concentration, the solution prepared is installed in brown shaking flask: select typical dye rhodamine B to be target contaminant, the solution prepared is installed in brown shaking flask;

The concentration of the rhodamine B described in step 2 is 20mg/L;

Install in brown shaking flask by the solution prepared described in step 2, in brown shaking flask, the volume of solution is 100mL;

Three, TOM-CoFe is added 2o 4: by TOM-CoFe 2o 4be added in step 2 and fully stir containing in the brown shaking flask of rhodamine B solution, keep reacting liquid temperature to be react 30min under the condition of 25 DEG C and pH=7, rhodamine B can be realized in waste water by TOM-CoFe 2o 4adsorption, and to obtain containing TOM-CoFe 2o 4solution.

TOM-CoFe described in step 3 2o 4dosage be 100mg/L;

Four, externally-applied magnetic field is adopted to be separated TOM-CoFe 2o 4: adopt externally-applied magnetic field to be separated TOM-CoFe 2o 4, the TOM-CoFe of recovery 2o 4carry out washing with ethanol and deionized water and 70 DEG C of vacuum-dryings, the TOM-CoFe of recovery 2o 4.Then complete and add TOM-CoFe separately 2o 4to the adsorption experiment of rhodamine B.

Experiment three: the experiment adding separately PMS oxidation rhodamine B is carried out by the following method:

One, prepare the waste water from dyestuff of prescribed concentration, the solution prepared is installed in brown shaking flask: select typical dye rhodamine B to be target contaminant, the solution prepared is installed in brown shaking flask.

The concentration of the rhodamine B described in step one is 20mg/L;

Install in brown shaking flask by the solution prepared described in step one, in brown shaking flask, the volume of solution is 100mL;

Two, persulphate is added: take persulphate by rhodamine B and the certain mol ratio of persulphate and be added in the brown shaking flask of step one and fully stir, reacting liquid temperature is kept to be under the condition of 25 DEG C and pH=7, reaction 30min, then complete and add separately the experiment that PMS is oxidized rhodamine B.

Persulphate described in step 2 is a kind of or wherein several mixture in Potassium peroxysulfate, single ammonium persulphate, single Sodium Persulfate and single persulfuric acid calcium.

Experiment four: spinel type CoFe 2o 4/ PMS technique is carried out by the following method to the degradation experiment of rhodamine B:

One, spinel type CoFe is prepared 2o 4;

by Co (NO 3) 26H 2o, Fe (NO 3) 39H 2o is dissolved in deionized water, is added drop-wise to by this dropwise in continuously stirring citric acid solution, under 60 DEG C of water bath condition, stirs 1h;

Step one described in Co (NO 3) 26H 2o, Fe (NO 3) 39H 2the mol ratio of O, citric acid is 1:2:8;

stirred solution is transferred to 90 DEG C of drying with water baths in beaker and obtains red gel, be transferred in crucible by this gel, and to place it in retort furnace roast 5h under 600 DEG C of conditions, after roast completes, material cooled is for subsequent use to room temperature storage;

Step one described in red gel is moved in crucible, and to place it in retort furnace roast 5h under 600 DEG C of conditions, the heat-up rate of retort furnace is 1 DEG C/min;

Two, prepare the waste water from dyestuff of prescribed concentration, the solution prepared is installed in brown shaking flask: select typical dye rhodamine B to be target contaminant, the solution prepared is installed in brown shaking flask;

The concentration of the rhodamine B described in step 2 is 20mg/L;

Install in brown shaking flask by the solution prepared described in step 2, in brown shaking flask, the volume of solution is 100mL;

Three, persulphate is added: take persulphate by the mol ratio that rhodamine B and persulphate are certain and be added in the brown shaking flask of step 2 and mix;

Persulphate described in step 3 is a kind of or wherein several mixture in Potassium peroxysulfate, single ammonium persulphate, single Sodium Persulfate and single persulfuric acid calcium;

In persulphate described in step 3 and pretreated waste water, the mol ratio of rhodamine B is 10:1;

Four, spinel type CoFe is added 2o 4: by spinel type CoFe 2o 4be added in step 3 and fully stir containing in the brown shaking flask of mixing solutions, keep reacting liquid temperature to be react 30min under the condition of 25 DEG C and pH=7, the removal of rhodamine B in waste water can be realized, and obtain containing spinel type CoFe 2o 4solution.Then complete spinel type CoFe 2o 4/ PMS technique is to the degradation experiment of rhodamine B.

Spinel type CoFe described in step 4 2o 4dosage be 100mg/L;

Experiment five: reuse number of times is to TOM-CoFe 2o 4the impact experiment of/PMS process degradation rhodamine B is carried out by the following method:

One, TOM-CoFe is prepared 2o 4;

by KIT-6 template, Co (NO 3) 26H 2o, Fe (NO 3) 39H 2o is put into successively in the mortar containing normal hexane and fully grinds, by the material transfer of fully grinding in the round-bottomed flask filling normal hexane, and return stirring 12h under 70 DEG C of water bath condition;

Step one described in KIT-6 template, Co (NO 3) 26H 2o, Fe (NO 3) 39H 2the mol ratio of O is 8:1:2;

Step one described in KIT-6 template, Co (NO 3) 26H 2o, Fe (NO 3) 39H 2o is put into successively in the mortar containing normal hexane and fully grinds, and the volume requirement of normal hexane above material can be flooded completely;

Step one described in by the material transfer of fully grinding in the round-bottomed flask filling normal hexane, return stirring 12h under 70 DEG C of water bath condition, the volume requirement of normal hexane above material can be flooded completely;

stirred solution is transferred in beaker, obtains pink solid at 70 DEG C of drying with water baths, by this solid transfer in crucible, and to place it in retort furnace roast 5h under 600 DEG C of conditions;

Step one described in pink solid is moved in crucible, and to place it in retort furnace roast 5h under 600 DEG C of conditions, the heat-up rate of retort furnace is 1 DEG C/min;

dark brown solid after roast is cooled to room temperature, is transferred in the round-bottomed flask of 2MNaOH solution after grinding evenly, under 70 DEG C of water bath condition, return stirring 24h is centrifugal after removing template, and above return stirring and centrifugation step repeat once;

Step one described in dark brown solid and the mass ratio of 2MNaOH solution be 1:(100 ~ 200);

Step one described in centrifugal used centrifuge speed be 8000r/min ~ 19000r/min;

after material after centrifugal uses deionized water and washing with alcohol to pH=7 respectively, 70 DEG C of vacuum-dryings obtain dark brown solid, store for future use after fully being ground by this solid;

Two, prepare the waste water from dyestuff of prescribed concentration, the solution prepared is installed in brown shaking flask: select typical dye rhodamine B to be target contaminant, the solution prepared is installed in brown shaking flask;

The concentration of the rhodamine B described in step 2 is 20mg/L;

Install in brown shaking flask by the solution prepared described in step 2, in brown shaking flask, the volume of solution is 100mL;

Three, persulphate is added: take persulphate by the mol ratio that rhodamine B and persulphate are certain and be added in the brown shaking flask of step 2 and mix;

Persulphate described in step 3 is a kind of or wherein several mixture in Potassium peroxysulfate, single ammonium persulphate, single Sodium Persulfate and single persulfuric acid calcium;

In persulphate described in step 3 and pretreated waste water, the mol ratio of rhodamine B is 10:1;

Four, the TOM-CoFe through externally-applied magnetic field recovery in step 5 is added 2o 4: the TOM-CoFe that externally-applied magnetic field is reclaimed 2o 4be added in step 3 and fully stir containing in the brown shaking flask of mixing solutions, keep reacting liquid temperature to be react 30min under the condition of 25 DEG C and pH=7, the efficient removal of rhodamine B in waste water can be realized, and obtain the TOM-CoFe containing reclaiming 2o 4solution;

The TOM-CoFe that externally-applied magnetic field described in step 4 reclaims 2o 4dosage be 100mg/L;

Five, externally-applied magnetic field is adopted to be separated TOM-CoFe 2o 4: adopt externally-applied magnetic field to be separated TOM-CoFe 2o 4, the TOM-CoFe of recovery 2o 4wash with ethanol and deionized water, and 70 DEG C of vacuum-dryings, the TOM-CoFe be recycled 2o 4.Utilize the TOM-CoFe reclaimed 2o 4carry out activation persulphate dye wastewater treatment.Then complete the TOM-CoFe of recovery 2o 4/ PMS technique is to the degradation experiment of rhodamine B.

Under different working condition rhodamine B concentration over time situation as shown in Figure 1, as we can see from the figure, TOM-CoFe 2o 4with under the condition that PMS coexists, reducing significantly has appearred in rhodamine B concentration in time, and clearance has exceeded 90%; Spinel type CoFe 2o 4with under the condition that PMS coexists, it is comparatively slow that rhodamine B concentration reduces in time, and clearance is only 50%; And add TOM-CoFe separately 2o 4time, in 30min, rhodamine B is only by TOM-CoFe 2o 4absorption is less than 5%; When adding separately PMS, in 30min, rhodamine B is only oxidized less than 10%.

Reuse number of times works in coordination with the impact of persulphate rhodamine B degradation as shown in Figure 2 to the order mesoporous cobalt ferrite of three-dimensional magnetic, TOM-CoFe after repeatedly reclaiming as can see from Figure 2 2o 4still very high catalytic performance is kept, the TOM-CoFe reclaimed for the 4th time 2o 4with under the condition that PMS coexists, in 30min, the clearance of rhodamine B is still up to about 80%.As can be seen here, TOM-CoFe 2o 4compared to spinel type CoFe 2o 4better catalytic activity is possessed to PMS, and TOM-CoFe 2o 4possesses good reuse.

Above-described embodiment is one of the present invention preferably scheme, not does any pro forma restriction to the present invention, also has other variant and remodeling under the prerequisite not exceeding the technical scheme described in claim.

Claims (7)

1., based on the method for three-dimensional magnetic order mesoporous cobalt ferrite activation persulphate dye wastewater treatment, it is characterized in that, described method is carried out according to the following steps:
One, the order mesoporous cobalt ferrite TOM-CoFe of three-dimensional magnetic is prepared 2o 4;
by KIT-6 template, Co (NO 3) 26H 2o, Fe (NO 3) 39H 2o is put into successively in the mortar containing normal hexane and fully grinds, by the material transfer of fully grinding in the round-bottomed flask filling appropriate normal hexane, and return stirring 12h under 70 DEG C of water bath condition;
stirred solution is transferred in beaker, obtains pink solid at 70-80 DEG C of drying with water bath, by this solid transfer in crucible, and to place it in retort furnace roast 5-5.5h under 600-650 DEG C of condition;
dark brown solid after roast is cooled to room temperature, and be transferred in the round-bottomed flask filling appropriate 2MNaOH solution after grinding evenly, under 70 DEG C of water bath condition, return stirring 24h is centrifugal after removing template, and above return stirring and centrifugation step repeat once;
after material after centrifugal uses deionized water and washing with alcohol to pH=7 respectively, 70-75 DEG C of vacuum-drying obtains dark brown solid, stores for future use after fully being ground by this solid;
Two, prepare the waste water from dyestuff of prescribed concentration, the solution prepared is installed in brown shaking flask;
Three, persulphate is added: take persulphate by the mol ratio that Wastewater Dyes and persulphate are certain and be added in the brown shaking flask of step 2 and mix;
Four, TOM-CoFe is added 2o 4: by TOM-CoFe 2o 4be added in step 3 and fully stir containing in the brown shaking flask of mixing solutions, keep reacting liquid temperature to be 20 ~ 50 DEG C and react 30min ~ 120min with pH under the condition of 3 ~ 9, realize the efficient removal of Wastewater Dyes, and obtain containing TOM-CoFe 2o 4solution;
Five, externally-applied magnetic field is adopted to be separated TOM-CoFe 2o 4: adopt externally-applied magnetic field to be separated TOM-CoFe 2o 4, the TOM-CoFe of recovery 2o 4carry out washing with ethanol and deionized water and 70-75 DEG C of vacuum-drying, the TOM-CoFe be recycled 2o 4.
2. the method based on three-dimensional magnetic order mesoporous cobalt ferrite activation persulphate dye wastewater treatment according to claim 1, is characterized in that:
Step one described in KIT-6 template, Co (NO 3) 26H 2o, Fe (NO 3) 39H 2the mol ratio of O is 8:1:2;
Step one described in KIT-6 template, Co (NO 3) 26H 2o, Fe (NO 3) 39H 2o is put into successively in the mortar containing normal hexane and fully grinds, and the volume requirement of normal hexane above material can be flooded completely;
Step one described in by the material transfer of fully grinding in the round-bottomed flask filling normal hexane, return stirring 12h under 70 DEG C of water bath condition, the volume requirement of normal hexane above material can be flooded completely.
3. the method based on three-dimensional magnetic order mesoporous cobalt ferrite activation persulphate dye wastewater treatment according to claim 1, is characterized in that: step one the heat-up rate of middle retort furnace is 1-1.2 DEG C/min.
4. the method based on three-dimensional magnetic order mesoporous cobalt ferrite activation persulphate dye wastewater treatment according to claim 1, is characterized in that:
Step one described in dark brown solid and the mass ratio of NaOH solution be 1:(100 ~ 200);
Step one described in centrifugal used centrifuge speed be 8000r/min ~ 19000r/min.
5. the method based on three-dimensional magnetic order mesoporous cobalt ferrite activation persulphate dye wastewater treatment according to claim 1, is characterized in that: in the waste water from dyestuff described in step 2, the concentration of dyestuff is 1mg/L ~ 200mg/L.
6. the method based on three-dimensional magnetic order mesoporous cobalt ferrite activation persulphate dye wastewater treatment according to claim 1, is characterized in that: the persulphate described in step 3 is a kind of or wherein several mixture in Potassium peroxysulfate, single ammonium persulphate, single Sodium Persulfate and single persulfuric acid calcium;
In persulphate described in step 3 and pretreated waste water, the mol ratio of dyestuff is (1 ~ 50): 1.
7. the method based on three-dimensional magnetic order mesoporous cobalt ferrite activation persulphate dye wastewater treatment according to claim 1, is characterized in that: the TOM-CoFe described in step 4 2o 4dosage be 10mg/L ~ 500mg/L.
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CN107117680A (en) * 2017-06-01 2017-09-01 徐靖才 The compound system and preparation method of a kind of rapidly and efficiently degradating organic dye
CN107840435A (en) * 2017-10-31 2018-03-27 徐靖才 A kind of compound system and preparation method of antibiotic of rapidly and efficiently degrading
US10843175B2 (en) * 2018-05-29 2020-11-24 Firouzeh Siadatnasab Composition and method for treating dye wastewater

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