CN105399197B - Method based on the order mesoporous cobalt ferrite activation persulfate processing waste water from dyestuff of three-dimensional magnetic - Google Patents

Method based on the order mesoporous cobalt ferrite activation persulfate processing waste water from dyestuff of three-dimensional magnetic Download PDF

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CN105399197B
CN105399197B CN201510928060.4A CN201510928060A CN105399197B CN 105399197 B CN105399197 B CN 105399197B CN 201510928060 A CN201510928060 A CN 201510928060A CN 105399197 B CN105399197 B CN 105399197B
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cofe
persulfate
tom
waste water
dyestuff
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CN105399197A (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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Huzhou Zhiqing Environmental Protection Technology Co ltd
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Zhejiang University of Technology ZJUT
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    • 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
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • 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
    • C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
    • C02F1/488—Treatment of water, waste water, or sewage with magnetic or electric fields for separation of magnetic materials, e.g. magnetic flocculation
    • 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
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents

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

Abstract

The invention discloses a kind of method based on the order mesoporous cobalt ferrite activation persulfate processing waste water from dyestuff of three-dimensional magnetic, it is intended to solves the problems, such as that existing spinel-type cobalt is relatively low to persulfate catalytic efficiency.The present invention is realized by following steps：First, the order mesoporous cobalt ferrite of three-dimensional magnetic is prepared；2nd, the waste water from dyestuff of prescribed concentration is prepared, the solution prepared is attached in brown shaking flask；3rd, persulfate is added；4th, the order mesoporous cobalt ferrite of three-dimensional magnetic is added；5th, the order mesoporous cobalt ferrite of three-dimensional magnetic is separated using externally-applied magnetic field, you can the method for completing a kind of order mesoporous cobalt ferrite activation persulfate processing Wastewater Dyes of three-dimensional magnetic.The efficient process of waste water from dyestuff can be realized using the order mesoporous cobalt ferrite collaboration persulfate technology of the three-dimensional magnetic of the present invention, clearance is more than 90%；Cobalt ions dissolution rate is extremely low during use, reduces environmental pollution；Catalyst can reduce operating cost by additional magnetic quick separating and recycling.

Description

Based on the order mesoporous cobalt ferrite activation persulfate processing waste water from dyestuff of three-dimensional magnetic Method
Technical field
The present invention relates to water treatment field, discloses a kind of based on the order mesoporous cobalt ferrite activation persulfate of three-dimensional magnetic The method for handling waste water from dyestuff.
Background technology
Different industries（Weaving, papermaking, leather, food, dyestuff manufacture etc.）The waste water from dyestuff of discharge is considered as water body dirt The important sources of dye.According to statistics, the total output about 1 of the annual dyestuff in the whole world, 000,000 ton.Waste water from dyestuff has that colourity is big, salt The features such as degree is high, biodegradability difference, if being directly discharged in water body to cause greatly to endanger to the mankind and environment.Rhodamine B It is a kind of important water-soluble xanthene organic dyestuff, more than half in the waste water of textile industry discharge contains the material.Sieve Red bright B presence can weaken the translucency of water body, reduce the dissolved oxygen amount in water, suppress the photosynthesis of aquatile, directly endanger The growth and existence of evil aquatile.What is more important, rhodamine B are a kind of suspicious carcinogens, complicated structure and Stable property makes it have suitable resistant function to biological treatment and light degradation, is discharged into water source to drink water to the mankind and pacifies Cause to seriously endanger entirely.Therefore, need badly and seek effective source and the pollution of rhodamine B in course control method for use solution water environment Problem.
In recent years, high-level oxidation technology is widely used in terms of water process, wherein based on potentiometric titrations （SO4 -) high-level oxidation technology receive significant attention.Transition metal ions activation persulfate (Peroxymonosufate, PMS reaction) can be carried out quickly at room temperature, without external energy（Thermal source and light source）, have broad application prospects.So And there is the problems such as catalyst recovery is difficult and easily initiation secondary environment pollutes in homogeneous persulfate catalyst system and catalyzing.It is and current Widely studied spinel-type cobalt is easy to reunite because specific surface area is smaller in water, greatly affected it to PMS Catalytic efficiency.For problem above, intend preparing the order mesoporous cobalt ferrite of three-dimensional magnetic by simple, economic method, in profit While with its unique architectural feature and interfacial characteristics efficient catalytic PMS, quick point of catalyst is realized by externally-applied magnetic field From.Method using the present invention can reach more than 90% to the clearance of difficult degradation organic dyestuff in water.
The content of the invention
Present invention seek to address that catalyst recovery is difficult in homogeneous persulfate catalyst system and catalyzing and easily causes the secondary of environment The problem of pollution and spinel-type cobalt catalytic performance are relatively low, it is proposed that one kind is based on the order mesoporous cobalt ferrite of three-dimensional magnetic The method for activating persulfate degradation of dye waste water.
The technical solution adopted for the present invention to solve the technical problems is：
Based on the method for the order mesoporous cobalt ferrite activation persulfate processing waste water from dyestuff of three-dimensional magnetic, enter according to the following steps OK：
First, the order mesoporous cobalt ferrite of three-dimensional magnetic is prepared（Three-dimensional ordered mesoporous CoFe2O4, TOM-CoFe2O4）；
By KIT-6 templates, Co (NO3)2·6H2O、Fe(NO3)3·9H2O is put into the mortar containing n-hexane successively It is fully ground, the material being fully ground is transferred in the round-bottomed flask for filling n-hexane, flows back and stir under 70 DEG C of water bath conditions Mix 12 h；
Step 1Described in KIT-6 templates, Co (NO3)2·6H2O、Fe(NO3)3·9H2O mol ratio is 8:1:2；
Step 1Described in KIT-6 templates, Co (NO3)2·6H2O、Fe(NO3)3·9H2O be put into successively containing just oneself It is fully ground in the mortar of alkane, the volume requirement of n-hexane is can to flood above material completely；
Step 1Described in the material being fully ground is transferred in the round-bottomed flask for filling n-hexane, at 70 DEG C The h of return stirring 12 under water bath condition, the volume requirement of n-hexane are can to flood above material completely；
Agitating solution is transferred in beaker, pink solid is obtained in 70-80 DEG C of drying with water baths, this solid is turned Move in crucible, and place it in the interior-5.5h of roast 5 under the conditions of 600-650 DEG C of Muffle furnace；
Step 1Described in pink solid is moved in crucible, and place it in Muffle furnace in 600-650 Roast 5-5.5h under the conditions of DEG C, the programming rate of Muffle furnace is 1-1.2 DEG C/min；
Dark brown solid after roast is cooled to room temperature, is transferred to after grinding uniformly and fills 2 M NaOH solutions Round-bottomed flask in, under 70 DEG C of water bath conditions the h of return stirring 24 remove template after centrifuge, above return stirring and centrifugation Step is repeated once；
Step 1Described in dark brown solid and 2 M NaOH solutions mass ratio be 1:(100~200)；
Step 1Described in centrifugation used in centrifuge speed be the r/min of 8000 r/min ~ 19000；
Material after centrifugation is washed to pH=7 with deionized water and ethanol respectively, and 70-75 DEG C is dried in vacuo To dark brown solid, stored for future use after this solid is fully ground；
2nd, the waste water from dyestuff of prescribed concentration is prepared, the solution prepared is attached in brown shaking flask：Select typical dye sieve Red bright B is target contaminant, and the solution prepared is attached in brown shaking flask；
The concentration of rhodamine B described in step 2 is the mg/L of 1 mg/L ~ 200；
The solution prepared is attached in brown shaking flask described in step 2, the volume of solution is 100 in brown shaking flask mL~200 mL；
3rd, persulfate is added：Persulfate is weighed by rhodamine B and the certain mol ratio of persulfate and is added to step It is well mixed in rapid two brown shaking flask；
Persulfate described in step 3 is Potassium peroxysulfate, single ammonium persulfate, single sodium peroxydisulfate and single persulfuric acid calcium In one kind or wherein several mixtures；
The mol ratio of rhodamine B is (1 ~ 50) in persulfate and pretreated waste water described in step 3:1；
4th, TOM-CoFe is added2O4：By TOM-CoFe2O4It is added in step 3 in the brown shaking flask containing mixed solution Be sufficiently stirred, keep reacting liquid temperature be 20 ~ 50 DEG C and pH be 3 ~ 9 under conditions of react the min of 30 min ~ 120, it is achievable to give up The efficient removal of rhodamine B in water, and obtain containing TOM-CoFe2O4Solution；
TOM-CoFe described in step 42O4Dosage be the mg/L of 10 mg/L ~ 500；
5th, TOM-CoFe is separated using externally-applied magnetic field2O4：TOM-CoFe is separated using externally-applied magnetic field2O4, the TOM- of recovery CoFe2O4Washed with ethanol and deionized water and in 70 DEG C of vacuum drying, the TOM-CoFe being recycled2O4。
The mechanism of this patent is that homogeneous persulfate system has catalyst recovery difficulty and easily causes secondary environmental pollution The problem of；And current spinel-type CoFe2O4Specific surface area is small（Usually less than 10 m2/g）, and be easy to reunite in the solution, Seriously reduce its catalytic capability to persulfate.And the TOM-CoFe of the use of the present invention2O4Possesses huge specific surface area With abundant pore structure, can preferably solve spinel-type CoFe2O4The problem of existing, so as to efficiently be catalyzed persulfuric acid Salt produces SO4-Degradable organic pollutant；In TOM-CoFe2O4Use during, Co2+Dissolution concentration it is extremely low, reduce pair The pollution of environment；TOM-CoFe2O4Magnetic ensure that it can quickly and easily be reclaimed by externally-applied magnetic field after the completion of reaction； And metal ion Co2+/Co3+Valence transition and persulfate decompose between balance ensure that catalyst continues efficiently to urge Change performance.
The present invention has the beneficial effect that：
1. TOM-CoFe2O4TOM-CoFe in/PMS systems2O4SO4 can be produced with efficient catalytic persulfate-, operation letter It is single, the energy is saved, without carrying out ultraviolet irradiation, ultrasonic cavitation, heating etc. to system；
2.TOM-CoFe2O4TOM-CoFe in/PMS systems2O4Possess huge specific surface area and abundant pore structure, It can be easier to contact with persulfate and organic dyestuff, be greatly enhanced catalytic efficiency；
3.TOM-CoFe2O4TOM-CoFe in/PMS systems2O4SO4 can be produced with efficient catalytic persulfate-Oxidative degradation Organic matter, clearance is more than 90%；
4. TOM-CoFe2O4TOM-CoFe in/PMS systems2O4With magnetic, recovery repetition can be carried out by externally-applied magnetic field Utilize, reduce operating cost.
Brief description of the drawings
Fig. 1 is rhodamine B concentration versus time curve under different working conditions.
WhereinShow and individually add TOM-CoFe2O4Under the conditions of rhodamine B concentration versus time curve；Wherein Expression individually adds rhodamine B concentration versus time curve under the conditions of PMS；Represent spinel-type CoFe2O4Collaboration Rhodamine B concentration versus time curve under conditions of PMS；Represent TOM-CoFe2O4Luo Dan under conditions of collaboration PMS Bright B concentration versus time curve.
Fig. 2 is reuse number to TOM-CoFe2O4Cooperate with the influence of PMS rhodamine B degradations.
Represent 0 TOM-CoFe of reuse2O4Rhodamine B concentration versus time curve under conditions of collaboration PMS；Represent the TOM-CoFe of reuse once2O4Rhodamine B concentration versus time curve under conditions of collaboration PMS； Represent the secondary TOM-CoFe of reuse2O4Rhodamine B concentration versus time curve under conditions of collaboration PMS；Represent back With three times with rhodamine B concentration versus time curve under conditions of collaboration PMS；The use collaboration that expression reuse is four times Rhodamine B concentration versus time curve under conditions of PMS.
Embodiment
Technical solution of the present invention is not limited to appointing between specific implementation method exemplified below, in addition to each embodiment Meaning combination.
Embodiment one：
It is a kind of in present embodiment that waste water from dyestuff is handled based on the order mesoporous cobalt ferrite activation persulfate of three-dimensional magnetic Method, carry out according to the following steps：
First, the order mesoporous cobalt ferrite of three-dimensional magnetic is prepared（Three-dimensional ordered mesoporous CoFe2O4, TOM-CoFe2O4）；
By KIT-6 templates, Co (NO3)2·6H2O、Fe(NO3)3·9H2O is put into the mortar containing n-hexane successively It is fully ground, the material being fully ground is transferred in the round-bottomed flask for filling n-hexane, flows back and stir under 70 DEG C of water bath conditions Mix 12 h；
Step 1Described in KIT-6 templates, Co (NO3)2·6H2O、Fe(NO3)3·9H2O mol ratio is 8:1:2；
Step 1Described in KIT-6 templates, Co (NO3)2·6H2O、Fe(NO3)3·9H2O be put into successively containing just oneself It is fully ground in the mortar of alkane, the volume requirement of n-hexane is can to flood above material completely；
Step 1Described in the material being fully ground is transferred in the round-bottomed flask for filling n-hexane, at 70 DEG C The h of return stirring 12 under water bath condition, the volume requirement of n-hexane are can to flood above material completely；
Agitating solution is transferred in beaker, pink solid is obtained in 70 DEG C of drying with water baths, this solid is shifted To crucible, and place it in the interior h of roast 5 under the conditions of 600 DEG C of Muffle furnace；
Step 1Described in pink solid is moved in crucible, and place it in Muffle furnace in 600 DEG C of bars The h of roast 5 under part, the programming rate of Muffle furnace is 1 DEG C/min；
Dark brown solid after roast is cooled to room temperature, 2 M NaOH solutions are transferred into after grinding uniformly Round-bottomed flask in, under 70 DEG C of water bath conditions the h of return stirring 24 remove template after centrifuge, above return stirring and centrifugation Step is repeated once；
Step 1Described in the mass ratio of dark brown solid and 2M NaOH solutions be 1:(100~200)；
Step 1Described in centrifugation used in centrifuge speed be the r/min of 8000 r/min ~ 19000；
Material after centrifugation is washed to pH=7 with deionized water and ethanol respectively, and 70 DEG C of vacuum drying obtain black Brown solid, stored for future use after this solid is fully ground；
2nd, the waste water from dyestuff of prescribed concentration is prepared, the solution prepared is attached in brown shaking flask：Select typical dye sieve Red bright B is target contaminant, and the solution prepared is attached in brown shaking flask.
The concentration of rhodamine B described in step 2 is the mg/L of 1 mg/L ~ 50；
The solution prepared is attached in brown shaking flask described in step 2, the volume of solution is 100 in brown shaking flask mL~200 mL；
3rd, persulfate is added：Persulfate is weighed by rhodamine B and the certain mol ratio of persulfate and is added to step It is well mixed in rapid two brown shaking flask；
Persulfate described in step 3 is Potassium peroxysulfate, single ammonium persulfate, single sodium peroxydisulfate and single persulfuric acid calcium In one kind or wherein several mixtures；
The mol ratio of rhodamine B is (20 ~ 50) in persulfate and pretreated waste water described in step 3:1；
4th, TOM-CoFe is added2O4：By TOM-CoFe2O4It is added in step 3 in the brown shaking flask containing mixed solution It is sufficiently stirred, it is that the min of 30 min ~ 120 is reacted under conditions of 20 ~ 30 DEG C and pH=3 ~ 6 to keep reacting liquid temperature, be can be achieved useless The efficient removal of rhodamine B in water, and obtain containing TOM-CoFe2O4Solution.
Three TOM-CoFe described in step 42O4Dosage be the mg/L of 10 mg/L ~ 100；
5th, TOM-CoFe is separated using externally-applied magnetic field2O4：TOM-CoFe is separated using externally-applied magnetic field2O4, the TOM- of recovery CoFe2O4Washed with ethanol and deionized water and in 70 DEG C of vacuum drying, the TOM-CoFe being recycled2O4。
Embodiment two：
Present embodiment is 50 from the concentration of target contaminant rhodamine B in step 2 unlike embodiment one The mg/L of mg/L ~ 100, other steps and parameter are identical with embodiment one.
Embodiment three：
The concentration of target contaminant rhodamine B in present embodiment step 2 unlike embodiment one to two For the mg/L of 100 mg/L ~ 200, other steps and parameter are identical with one of embodiment one to two.
Embodiment four：
Present embodiment step 3 persulfate and target contaminant unlike embodiment one to three rub Your ratio is (1 ~ 20):1.Other steps and parameter are identical with one of embodiment one to three.
Embodiment five：
TOM-CoFe in step 4 unlike one of present embodiment and embodiment one to four2O4Dosage For the mg/L of 100 mg/L ~ 300.Other steps and parameter are identical with one of embodiment one to four.
Embodiment six：
TOM-CoFe in step 4 unlike one of present embodiment and embodiment one to five2O4Dosage For the mg/L of 300 mg/L ~ 500.Other steps and parameter are identical with one of embodiment one to five.
Embodiment seven：
Temperature of reaction system is 30 DEG C in step 4 unlike one of present embodiment and embodiment one to six ~50 ℃.Other steps and parameter are identical with one of embodiment one to six.
Embodiment eight：
Reaction system pH is 6 ~ 9 in step 4 unlike one of present embodiment and embodiment one to seven.Its His step and parameter are identical with one of embodiment one to seven.
Embodiment nine：
The TOM-CoFe added in step 4 unlike one of present embodiment and embodiment one to eight2O4For The TOM-CoFe reclaimed in step 5 by externally-applied magnetic field2O4.One of other steps and parameter and embodiment one to eight phase Together.
In order to verify beneficial effects of the present invention, following experiment has been carried out：
Experiment one：
One kind is based on TOM-CoFe2O4/ PMS techniques are carried out by the following method to the degradation experiment of rhodamine B：
First, TOM-CoFe is prepared2O4；
By KIT-6 templates, Co (NO3)2·6H2O、Fe(NO3)3·9H2O is put into the mortar containing n-hexane successively It is fully ground, the material being fully ground is transferred in the round-bottomed flask for filling n-hexane, flows back and stir under 70 DEG C of water bath conditions Mix 12 h；
Step 1Described in KIT-6 templates, Co (NO3)2·6H2O、Fe(NO3)3·9H2O mol ratio is 8:1:2；
Step 1Described in KIT-6 templates, Co (NO3)2·6H2O、Fe(NO3)3·9H2O be put into successively containing just oneself It is fully ground in the mortar of alkane, the volume requirement of n-hexane is can to flood above material completely；
Step 1Described in the material being fully ground is transferred in the round-bottomed flask for filling n-hexane, at 70 DEG C The h of return stirring 12 under water bath condition, the volume requirement of n-hexane are can to flood above material completely；
Agitating solution is transferred in beaker, pink solid is obtained in 70 DEG C of drying with water baths, this solid is shifted To crucible, and place it in the interior h of roast 5 under the conditions of 600 DEG C of Muffle furnace；
Step 1Described in pink solid is moved in crucible, and place it in Muffle furnace in 600 DEG C of bars The h of roast 5 under part, the programming rate of Muffle furnace is 1 DEG C/min；
Dark brown solid after roast is cooled to room temperature, 2 M NaOH solutions are transferred into after grinding uniformly Round-bottomed flask in, under 70 DEG C of water bath conditions the h of return stirring 24 remove template after centrifuge, above return stirring and centrifugation Step is repeated once；
Step 1Described in dark brown solid and 2 M NaOH solutions mass ratio be 1:(100~200)；
Step 1Described in centrifugation used in centrifuge speed be the r/min of 8000 r/min ~ 19000；
Material after centrifugation is washed to pH=7 with deionized water and ethanol respectively, is obtained in 70 DEG C of vacuum drying Dark brown solid, stored for future use after this solid is fully ground；
2nd, the waste water from dyestuff of prescribed concentration is prepared, the solution prepared is attached in brown shaking flask：Select typical dye sieve Red bright B is target contaminant, and the solution prepared is attached in brown shaking flask；
The concentration of rhodamine B described in step 2 is 20 mg/L；
The solution prepared is attached in brown shaking flask described in step 2, the volume of solution is 100 in brown shaking flask mL；
3rd, persulfate is added：Persulfate is weighed by rhodamine B and the certain mol ratio of persulfate and is added to step It is well mixed in rapid two brown shaking flask；
Persulfate described in step 3 is Potassium peroxysulfate, single ammonium persulfate, single sodium peroxydisulfate and single persulfuric acid calcium In one kind or wherein several mixtures；
The mol ratio of rhodamine B is 10 in persulfate and pretreated waste water described in step 3:1；
4th, TOM-CoFe is added2O4：By TOM-CoFe2O4It is added in step 3 in the brown shaking flask containing mixed solution It is sufficiently stirred, keeps reacting liquid temperature to react 30 min under conditions of 25 DEG C and pH=7, rhodamine B in waste water can be achieved Efficiently remove, and obtain containing TOM-CoFe2O4Solution.
TOM-CoFe described in step 42O4Dosage be 100 mg/L；
5th, TOM-CoFe is separated using externally-applied magnetic field2O4：TOM-CoFe is separated using externally-applied magnetic field2O4, the TOM- of recovery CoFe2O4Washed with ethanol and deionized water and in 70 DEG C of vacuum drying, the TOM-CoFe of recovery2O4.Then complete TOM-CoFe2O4Degradation experiment of/PMS the techniques to rhodamine B.
Experiment two：Individually add TOM-CoFe2O4The experiment of absorption rhodamine B is carried out by the following method：
First, TOM-CoFe is prepared2O4；
By KIT-6 templates, Co (NO3)2·6H2O、Fe(NO3)3·9H2O is put into the mortar containing n-hexane successively It is fully ground, the material being fully ground is transferred in the round-bottomed flask for filling n-hexane, flows back and stir under 70 DEG C of water bath conditions Mix 12 h；
Step 1Described in KIT-6 templates, Co (NO3)2·6H2O、Fe(NO3)3·9H2O mol ratio is 8:1:2；
Step 1Described in KIT-6 templates, Co (NO3)2·6H2O、Fe(NO3)3·9H2O be put into successively containing just oneself It is fully ground in the mortar of alkane, the volume requirement of n-hexane is can to flood above material completely；
Step 1Described in the material being fully ground is transferred in the round-bottomed flask for filling n-hexane, at 70 DEG C The h of return stirring 12 under water bath condition, the volume requirement of n-hexane are can to flood above material completely；
Agitating solution is transferred in beaker, pink solid is obtained in 70 DEG C of drying with water baths, this solid is shifted To crucible, and place it in the interior h of roast 5 under the conditions of 600 DEG C of Muffle furnace；
Step 1Described in pink solid is moved in crucible, and place it in Muffle furnace in 600 DEG C of bars The h of roast 5 under part, the programming rate of Muffle furnace is 1 DEG C/min；
Dark brown solid after roast is cooled to room temperature, 2 M NaOH solutions are transferred into after grinding uniformly Round-bottomed flask in, under 70 DEG C of water bath conditions the h of return stirring 24 remove template after centrifuge, above return stirring and centrifugation Step is repeated once；
Step 1Described in dark brown solid and 2 M NaOH solutions mass ratio be 1:(100~200)；
Step 1Described in centrifugation used in centrifuge speed be the r/min of 8000 r/min ~ 19000；
Material after centrifugation is washed to pH=7 with deionized water and ethanol respectively, is obtained in 70 DEG C of vacuum drying Dark brown solid, stored for future use after this solid is fully ground；
2nd, the waste water from dyestuff of prescribed concentration is prepared, the solution prepared is attached in brown shaking flask：Select typical dye sieve Red bright B is target contaminant, and the solution prepared is attached in brown shaking flask；
The concentration of rhodamine B described in step 2 is 20 mg/L；
The solution prepared is attached in brown shaking flask described in step 2, the volume of solution is 100 in brown shaking flask mL；
3rd, TOM-CoFe is added2O4：By TOM-CoFe2O4The brown containing rhodamine B solution in step 2 is added to shake It is sufficiently stirred in bottle, keeps reacting liquid temperature that rhodamine in waste water can be achieved to react 30 min under conditions of 25 DEG C and pH=7 B is by TOM-CoFe2O4Adsorption, and obtain containing TOM-CoFe2O4Solution.
TOM-CoFe described in step 32O4Dosage be 100 mg/L；
4th, TOM-CoFe is separated using externally-applied magnetic field2O4：TOM-CoFe is separated using externally-applied magnetic field2O4, the TOM- of recovery CoFe2O4Washed with ethanol and deionized water and in 70 DEG C of vacuum drying, the TOM-CoFe of recovery2O4.Then complete list Solely add TOM-CoFe2O4To the adsorption experiment of rhodamine B.
Experiment three：The experiment for individually adding PMS oxidation rhodamine Bs is carried out by the following method：
First, the waste water from dyestuff of prescribed concentration is prepared, the solution prepared is attached in brown shaking flask：Select typical dye sieve Red bright B is target contaminant, and the solution prepared is attached in brown shaking flask.
The concentration of rhodamine B described in step 1 is 20 mg/L；
The solution prepared is attached in brown shaking flask described in step 1, the volume of solution is 100 in brown shaking flask mL；
2nd, persulfate is added：Persulfate is weighed by rhodamine B and the certain mol ratio of persulfate and is added to step Be sufficiently stirred in rapid one brown shaking flask, under conditions of keeping reacting liquid temperature as 25 DEG C and pH=7, react 30 min, then it is complete Into the experiment for individually adding PMS oxidation rhodamine Bs.
Persulfate described in step 2 is Potassium peroxysulfate, single ammonium persulfate, single sodium peroxydisulfate and single persulfuric acid calcium In one kind or wherein several mixtures.
Experiment four：Spinel-type CoFe2O4/ PMS techniques are carried out by the following method to the degradation experiment of rhodamine B：
First, spinel-type CoFe is prepared2O4；
By Co (NO3)2·6H2O、Fe(NO3)3·9H2O is dissolved into deionized water, by the solution company of being added drop-wise to dropwise In continuous stirring citric acid solution, 1 h is stirred under 60 DEG C of water bath conditions；
Step 1Described in Co (NO3)2·6H2O、Fe(NO3)3·9H2O, the mol ratio of citric acid is 1:2:8；
Agitating solution is transferred to 90 DEG C of drying with water baths in beaker and obtains red gel, this gel is transferred to crucible It is interior, and the interior h of roast 5 under the conditions of 600 DEG C of Muffle furnace is placed it in, it is standby to be cooled to room temperature storage for material after the completion of roast With；
Step 1Described in red gel is moved in crucible, and place it in Muffle furnace in 600 DEG C of conditions The lower h of roast 5, the programming rate of Muffle furnace is 1 DEG C/min；
2nd, the waste water from dyestuff of prescribed concentration is prepared, the solution prepared is attached in brown shaking flask：Select typical dye sieve Red bright B is target contaminant, and the solution prepared is attached in brown shaking flask；
The concentration of rhodamine B described in step 2 is 20 mg/L；
The solution prepared is attached in brown shaking flask described in step 2, the volume of solution is 100 in brown shaking flask mL；
3rd, persulfate is added：Persulfate is weighed by rhodamine B and the certain mol ratio of persulfate and is added to step It is well mixed in rapid two brown shaking flask；
Persulfate described in step 3 is Potassium peroxysulfate, single ammonium persulfate, single sodium peroxydisulfate and single persulfuric acid calcium In one kind or wherein several mixtures；
The mol ratio of rhodamine B is 10 in persulfate and pretreated waste water described in step 3:1；
4th, spinel-type CoFe is added2O4：By spinel-type CoFe2O4It is added to the palm fibre containing mixed solution in step 3 It is sufficiently stirred in color shaking flask, keeps reacting liquid temperature that sieve in waste water can be achieved to react 30 min under conditions of 25 DEG C and pH=7 Red bright B removal, and obtain containing spinel-type CoFe2O4Solution.Then complete spinel-type CoFe2O4/ PMS techniques pair The degradation experiment of rhodamine B.
Spinel-type CoFe described in step 42O4Dosage be 100 mg/L；
Experiment five：Reuse number is to TOM-CoFe2O4The influence experiment of/PMS process degradation rhodamine Bs is entered by the following method OK：
First, TOM-CoFe is prepared2O4；
By KIT-6 templates, Co (NO3)2·6H2O、Fe(NO3)3·9H2O is put into the mortar containing n-hexane successively It is fully ground, the material being fully ground is transferred in the round-bottomed flask for filling n-hexane, flows back and stir under 70 DEG C of water bath conditions Mix 12 h；
Step 1Described in KIT-6 templates, Co (NO3)2·6H2O、Fe(NO3)3·9H2O mol ratio is 8:1:2；
Step 1Described in KIT-6 templates, Co (NO3)2·6H2O、Fe(NO3)3·9H2O be put into successively containing just oneself It is fully ground in the mortar of alkane, the volume requirement of n-hexane is can to flood above material completely；
Step 1Described in the material being fully ground is transferred in the round-bottomed flask for filling n-hexane, at 70 DEG C The h of return stirring 12 under water bath condition, the volume requirement of n-hexane are can to flood above material completely；
Agitating solution is transferred in beaker, pink solid is obtained in 70 DEG C of drying with water baths, this solid is shifted To crucible, and place it in the interior h of roast 5 under the conditions of 600 DEG C of Muffle furnace；
Step 1Described in pink solid is moved in crucible, and place it in Muffle furnace in 600 DEG C of bars The h of roast 5 under part, the programming rate of Muffle furnace is 1 DEG C/min；
Dark brown solid after roast is cooled to room temperature, 2 M NaOH solutions are transferred into after grinding uniformly Round-bottomed flask in, under 70 DEG C of water bath conditions the h of return stirring 24 remove template after centrifuge, above return stirring and centrifugation Step is repeated once；
Step 1Described in dark brown solid and 2 M NaOH solutions mass ratio be 1:(100~200)；
Step 1Described in centrifugation used in centrifuge speed be the r/min of 8000 r/min ~ 19000；
Material after centrifugation is washed to pH=7 with deionized water and ethanol respectively, and 70 DEG C of vacuum drying obtain black Brown solid, stored for future use after this solid is fully ground；
2nd, the waste water from dyestuff of prescribed concentration is prepared, the solution prepared is attached in brown shaking flask：Select typical dye sieve Red bright B is target contaminant, and the solution prepared is attached in brown shaking flask；
The concentration of rhodamine B described in step 2 is 20 mg/L；
The solution prepared is attached in brown shaking flask described in step 2, the volume of solution is 100 in brown shaking flask mL；
3rd, persulfate is added：Persulfate is weighed by rhodamine B and the certain mol ratio of persulfate and is added to step It is well mixed in rapid two brown shaking flask；
Persulfate described in step 3 is Potassium peroxysulfate, single ammonium persulfate, single sodium peroxydisulfate and single persulfuric acid calcium In one kind or wherein several mixtures；
The mol ratio of rhodamine B is 10 in persulfate and pretreated waste water described in step 3:1；
4th, the TOM-CoFe reclaimed in step 5 through externally-applied magnetic field is added2O4：The TOM-CoFe that externally-applied magnetic field is reclaimed2O4 It is added in step 3 in the brown shaking flask containing mixed solution and is sufficiently stirred, it is 25 DEG C and pH=7 to keep reacting liquid temperature Under the conditions of react 30 min, can be achieved waste water in rhodamine B efficient removal, and obtain containing reclaim TOM-CoFe2O4It is molten Liquid；
The TOM-CoFe of externally-applied magnetic field recovery described in step 42O4Dosage be 100 mg/L；
5th, TOM-CoFe is separated using externally-applied magnetic field2O4：TOM-CoFe is separated using externally-applied magnetic field2O4, the TOM- of recovery CoFe2O4Washed with ethanol and deionized water, and in 70 DEG C of vacuum drying, the TOM-CoFe being recycled2O4.Using return The TOM-CoFe of receipts2O4Carry out activating persulfate processing waste water from dyestuff.Then complete the TOM-CoFe of recovery2O4/ PMS techniques To the degradation experiment of rhodamine B.
Under different working conditions rhodamine B concentration change with time situation as shown in figure 1, from the figure, it can be seen that TOM-CoFe2O4Under conditions of being coexisted with PMS, rhodamine B concentration occurs significantly reducing with the time, and clearance exceedes 90%；Spinel-type CoFe2O4Under conditions of being coexisted with PMS, rhodamine B concentration with the time reduce more slowly, clearance is only For 50%；And individually add TOM-CoFe2O4When, rhodamine B is only by TOM-CoFe in 30 min2O4Absorption is less than 5%;Individually throw When adding PMS, rhodamine B has only been oxidized less than 10% in 30 min.
Reuse number cooperates with influence such as Fig. 2 institutes of persulfate rhodamine B degradation to the order mesoporous cobalt ferrite of three-dimensional magnetic Show, TOM-CoFe after repeatedly reclaiming as can see from Figure 22O4Remain in that very high catalytic performance, the TOM- of the 4th recovery CoFe2O4Under conditions of being coexisted with PMS, the clearance of rhodamine B is still up to 80% or so in 30 min.As can be seen here, TOM- CoFe2O4Compared to spinel-type CoFe2O4Possess more preferable catalytic activity, and TOM-CoFe to PMS2O4Possesses good reuse Property.
Embodiment described above is a kind of preferable scheme of the present invention, not the present invention is made any formal Limitation, there are other variants and remodeling on the premise of without departing from the technical scheme described in claim.

Claims (6)

1. the method based on the order mesoporous cobalt ferrite activation persulfate processing waste water from dyestuff of three-dimensional magnetic, it is characterised in that institute Method is stated to carry out according to the following steps：
First, the order mesoporous cobalt ferrite TOM-CoFe of three-dimensional magnetic is prepared2O4；
1. by KIT-6 templates, Co (NO3)2·6H2O、Fe(NO3)3·9H2O is put into the mortar containing n-hexane and fully ground successively Mill, the material being fully ground is transferred in the round-bottomed flask for filling appropriate n-hexane, the return stirring under 70 DEG C of water bath conditions 12h；
2. agitating solution is transferred in beaker, pink solid is obtained in 70-80 DEG C of drying with water bath, this solid is transferred to earthenware In crucible, and place it in the interior roast 5-5.5h under the conditions of 600-650 DEG C of Muffle furnace；
3. the dark brown solid after roast is cooled into room temperature, it is transferred to after grinding uniformly and fills appropriate 2M NaOH solutions In round-bottomed flask, return stirring 24h is centrifuged after removing template under 70 DEG C of water bath conditions, above return stirring and centrifugation step It is repeated once；
4. the material after centrifugation is washed to pH=7 with deionized water and ethanol respectively, 70-75 DEG C of vacuum drying obtains dark brown Color solid, stored for future use after this solid is fully ground；
2nd, the waste water from dyestuff of prescribed concentration is prepared, the solution prepared is attached in brown shaking flask；
3rd, persulfate is added：Persulfate is weighed by Wastewater Dyes and the certain mol ratio of persulfate and is added to step It is well mixed in rapid two brown shaking flask；
4th, TOM-CoFe is added2O4：By TOM-CoFe2O4It is added in step 3 in the brown shaking flask containing mixed solution fully Stirring, keep reacting liquid temperature be 20~50 DEG C and pH be 3~9 under conditions of react 30min~120min, realize in waste water and contaminate The efficient removal of material, and obtain containing TOM-CoFe2O4Solution；
5th, TOM-CoFe is separated using externally-applied magnetic field2O4：TOM-CoFe is separated using externally-applied magnetic field2O4, the TOM- of recovery CoFe2O4Washed with ethanol and deionized water and in 70-75 DEG C of vacuum drying, the TOM-CoFe being recycled2O4；
Step 1 1. described in KIT-6 templates, Co (NO3)2·6H2O、Fe(NO3)3·9H2O mol ratio is 8: 1: 2；
Step 1 1. described in KIT-6 templates, Co (NO3)2·6H2O、Fe(NO3)3·9H2O is put into containing n-hexane successively It is fully ground in mortar, the volume requirement of n-hexane is can to flood above material completely；
Step 1 1. described in the material being fully ground is transferred in the round-bottomed flask for filling n-hexane, in 70 DEG C of water-bath bars Return stirring 12h under part, the volume requirement of n-hexane are can to flood above material completely.
2. according to claim 1 handle waste water from dyestuff based on the order mesoporous cobalt ferrite activation persulfate of three-dimensional magnetic Method, it is characterised in that：The programming rate of step 1 2. middle Muffle furnace is 1-1.2 DEG C/min.
3. according to claim 1 handle waste water from dyestuff based on the order mesoporous cobalt ferrite activation persulfate of three-dimensional magnetic Method, it is characterised in that：
Step 1 3. described in dark brown solid and NaOH solution mass ratio be 1: (100~200)；
Step 1 3. described in centrifugation used in centrifuge speed be 8000r/min~19000r/min.
4. according to claim 1 handle waste water from dyestuff based on the order mesoporous cobalt ferrite activation persulfate of three-dimensional magnetic Method, it is characterised in that：The concentration of dyestuff is 1mg/L~200mg/L in waste water from dyestuff described in step 2.
5. according to claim 1 handle waste water from dyestuff based on the order mesoporous cobalt ferrite activation persulfate of three-dimensional magnetic Method, it is characterised in that：Persulfate described in step 3 is Potassium peroxysulfate, single ammonium persulfate, single sodium peroxydisulfate and list One kind or wherein several mixtures in persulfuric acid calcium；
The mol ratio of dyestuff is (1~50) in persulfate and pretreated waste water described in step 3: 1.
6. according to claim 1 handle waste water from dyestuff based on the order mesoporous cobalt ferrite activation persulfate of three-dimensional magnetic Method, it is characterised in that：TOM-CoFe described in step 42O4Dosage be 10mg/L~500mg/L.
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