CN102350296A - Preparation method of magnetic mesoporous adsorption material for cationic dye - Google Patents
Preparation method of magnetic mesoporous adsorption material for cationic dye Download PDFInfo
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- CN102350296A CN102350296A CN2011103283441A CN201110328344A CN102350296A CN 102350296 A CN102350296 A CN 102350296A CN 2011103283441 A CN2011103283441 A CN 2011103283441A CN 201110328344 A CN201110328344 A CN 201110328344A CN 102350296 A CN102350296 A CN 102350296A
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Abstract
The invention provides a preparation method of a magnetic mesoporous adsorption material for a cationic dye, and belongs to the technical field of adsorption material preparation. The method comprises the following steps: performing a chemical reaction between soluble cobalt salt and ferrous salt aqueous solution with a certain concentration and oxalic acid (salt) aqueous solution with a certain concentration to prepare a composite metal oxalate precursor; calcining the synthesized composite metal oxalate precursor under a process control condition to obtain a magnetic mesoporous oxide; and hydrothermally activating the magnetic mesoporous oxide with a sodium citrate aqueous solution to obtain the magnetic mesoporous adsorption material for the cationic dye. The method has the advantages that: after hydrothermal activation, the mesoporous magnetic material prepared by the composite metal oxalate precursor has strong specific adsorption, high adsorption efficiency and good adsorption effect to the cationic dye. The method can realize solid and liquid separation under the action of a magnetic field, is simple and controllable, and is easy for large-scale industrial production.
Description
Technical field
The invention belongs to the sorbing material preparing technical field, be specifically related to the preparation method of the magnetic mesoporous sorbing material of a kind of cationic dyes.
Background technology
Dyeing waste water complicated component, mass concentration are high, colourity is dark and discharge capacity is big, have complex structure, fast lightly separate, characteristics such as resistance to oxidation, have become important pollution sources.In case enter the water body of surrounding environment by all means, cause serious harm with the direct or indirect destruction ecological balance and to human health.According to estimates, account for 15% of whole world gross contamination emission without the dyestuff of dealing carefully with regard to being discharged in the environment.How to solve the problem of environmental pollution that waste water from dyestuff causes effectively and become the task of top priority.Yet waste water containing dye is difficult to biochemical degradation, and very difficulty is handled in decolouring.Domestic dye wastewater treatment using is main with bioanalysis.The shortcoming of bioanalysis is that chroma removal rate is low, and most dyestuff biodegradability is poor, and the existence of the inorganic yin, yang ion of part also possibly cause biotoxication and inactivation in the dyestuff.The biological effluent treatment that other is traditional, very limited to the decolored degradation of waste water from dyestuff like activated sludge process, biomembrance process, anaerobic bio-treated method, physico-chemical process dye wastewater treatment using cost is too high, in practical application, is difficult to obtain promote.
Absorption method has simple to operate, low cost and other advantages aspect the difficult degradation pollutant in removing water, be with a wide range of applications.The sorbing material that current usefulness removes heavy metal ions in wastewater mainly is silicon material, carbon material, zeolite and modification body thereof, ion exchange resin, complexing resin, porous polymer bead etc.; But these materials exist or adsorption efficiency is low, capacity is little; Or defectives such as the scope of application is little, reproducibility is poor, cost height; Sorbing material and mother liquor difficult separation and recycling in addition, complex operation.Document (1) " Journal of Hazardous Materials 2008; 160; 643 ", document (2) " Journal of Hazardous Materials 2009; 167,383 " propose: through with sorbing material and the compound sorbing material magnetic of giving of magnetic oxide, realize that adsorbent separates and reuse with the controlled of feed liquid.Document (3) " Journal of Hazardous Materials 2009; 163; 174 ", document (4) " Journal of Hazardous Materials; 2010,181,586 " propose: through magnetic particle is modified the preparation magnetic adsorbent through immobilized reaction with organo-functional group.Preparation method's complex steps that above document is announced, the industrialization cost is high, is difficult to realize the large-scale industrial application.
Summary of the invention
The present invention is directed to the technical problem that prior art exists; From reducing the sorbing material preparation cost and being convenient to recycle two aspects; The preparation method of the magnetic mesoporous sorbing material of a kind of cationic dyes is provided, and the sorbing material of this method preparation is strong to the cationic dyes specificity, adsorption efficiency is high, advantages of good adsorption effect.
Preparation method's concrete steps of the magnetic mesoporous sorbing material of a kind of cationic dyes provided by the present invention are following:
(1) with certain density solubility cobalt salt, the divalent iron salt aqueous solution and after the certain density oxalic acid aqueous solution or the oxalates aqueous solution mix in reactor; Leave standstill heavyization; The mol ratio of said solubility cobalt salt and divalent iron salt is 1:2, and the mol ratio of solubility cobalt salt and divalent iron salt and oxalate denominationby is 1: (1～3), reaction temperature are 20～50 ℃; After leaving standstill heavyization 2～10h, feed liquid is made magnetic mesoporous sorbing material predecessor after dehydration, drying;
(2) the magnetic mesoporous sorbing material predecessor that step (1) is made is calcined under air atmosphere, 1～5 ℃/min of heating rate, and 300～500 ℃ of calcining heats obtain calcined product behind calcining 2～4h;
(3) the calcined product hydro-thermal activation in sodium citrate aqueous solution that step (2) is obtained; Promptly get the exclusive magnetic adsorptive material of the dye of positive ion; The mol ratio of said calcined product and natrium citricum is 1: (3～8); Activation temperature is 80～150 ℃, obtains the magnetic mesoporous sorbing material of said cationic dyes behind hydro-thermal activation 4～10h.
Said solubility cobalt salt is a kind of in cobalt chloride, cobaltous sulfate and the cobalt nitrate;
Described divalent iron salt is a kind of in frerrous chloride, ferrous sulfate and the iron ammonium sulfate;
Described oxalates is sodium oxalate or potassium oxalate.
The heating mode that calcination process adopted is a programmed temperature method.
The mechanism of action of the inventive method is following: ferric oxalate cobalt precursor air atmosphere calcining down obtains the magnetic oxide cobalt ferrite; Discharge carbon monoxide, carbon dioxide, water etc. in the ferric oxalate cobalt precursor calcination process, produce a large amount of meso-hole structures in the oxide particle; The strong complexing of citrate ion makes oxide surface part metals ion come off, and gets into solution.The aggravation of magnetic oxide yin, yang ionic charge, negative electrical charge is superfluous.Adsorbent produces specificity absorption through electrostatic interaction to cationic dyes.
Beneficial effect that the present invention has and outstanding advantage are:
Through the ion deposition of solubility cobalt salt, divalent iron salt and oxalic acid (salt), low temperature synthesizes composition metal oxalates presoma in the aqueous solution; Adopt stored program control system to obtain mesoporous magnetic composite oxides; The activation of mesoporous magnetic composite oxides hydro-thermal.Make mesoporous magnetic material with composition metal oxalates presoma, after the hydro-thermal activation, cationic dyes is had exclusive adsorptivity, can under the effect of magnetic field, realize Separation of Solid and Liquid.Directly with magnetic particle as the sorbing material dye wastewater treatment using, no matter from preparation technology, cost still be the water treatment applications to the equal tool clear superiority of controlling of solid-liquid, be easy to realize large-scale industrial production and application.
Description of drawings
Figure: the XRD figure spectrum of the activation products of three embodiment preparations of the present invention.
The specific embodiment
Embodiment 1: 19.8g frerrous chloride, 11.9g cobalt chloride fully are dissolved in the 1L water, in addition the 20.1g sodium oxalate are dissolved in the same volume ponding; Sodium oxalate solution is added in ferrous iron, the cobalt mixed liquor, stir, reaction temperature is 20 ℃, and under this temperature still aging 10h, feed liquid suction filtration dehydration then, 100 ℃ of forced air drying 4h in the filter cake air.The filter cake of drying is placed Muffle furnace, be warming up to 300 ℃, insulation 4h with the speed of 1 ℃/min.After treating that furnace temperature is cooled to room temperature, get 4g filter cake and 24g natrium citricum and add 120 ℃ of hydro-thermal 7h of the aqueous solution in the 0.2L agitated reactor, wait solution to be cooled to room temperature after, the dehydration of feed liquid suction filtration, 100 ℃ of forced air drying 4h obtain the exclusive sorbing material of the dye of positive ion of the present invention.Adopt X-ray diffraction with D8 Advance diffractometer (CuK α) radiation, its XRD test result is as shown in Figure 1, and product is the single spinel-type ferrous acid cobalt of crystalline phase.With He is carrier gas, adopts Micromeritics Tristar 3000 type specific surface analyzers to carry out N
2Its meso-hole structure is measured in the test of absorption～desorption.
The product that obtains is used for the wastewater treatment of cation dyestuff methylene blue, anionic dye methyl orange, and the result shows: at waste strength is 40mg/L, and the adsorbent consumption is 2.5g/L, adds that the methylene blue clearance is 99.2% behind the adsorbent 5min; Can realize Separation of Solid and Liquid easily with magnet.Anionic dye methyl orange there is not suction-operated.
Embodiment 2: 27.8g ferrous sulfate, 14.6g cobalt nitrate fully are dissolved in the 1L water, in addition 37.8g oxalic acid are dissolved in the same volume ponding; Oxalic acid solution is added in the mixed liquor of ferrous iron, cobalt salt, stir, reaction temperature is 35 ℃, and under this temperature still aging 5h, feed liquid suction filtration dehydration then, 100 ℃ of forced air drying 4h in the filter cake air.The filter cake of drying is placed Muffle furnace, be warming up to 400 ℃, insulation 3h with the speed of 5 ℃/min.After treating that furnace temperature is cooled to room temperature, get 4g filter cake and 32g natrium citricum and add 80 ℃ of hydro-thermal 10h in the 0.2L reactant aqueous solution still, wait solution to be cooled to room temperature after, the dehydration of feed liquid suction filtration, 100 ℃ of forced air drying 4h obtain the exclusive sorbing material of the dye of positive ion of the present invention.Material characterizes with embodiment 1.
The product that obtains is used for the wastewater treatment of cation dyestuff crystal violet, anionic dye methyl orange, and the result shows: at waste strength is 40mg/L, and the adsorbent consumption is 2.0g/L, adds that the crystal violet clearance is 98.5% behind the adsorbent 5min; Magnet can be realized Separation of Solid and Liquid easily.Anionic dye methyl orange there is not suction-operated.
Embodiment 3: 39.2g iron ammonium sulfate, 14.1g cobaltous sulfate fully are dissolved in the 1L water, in addition the 27.7g potassium oxalate are dissolved in the same volume ponding; Potassium Oxalate Solution is added in ferrous iron, the cobalt mixed liquor, stir, reaction temperature is 50 ℃, and under this temperature still aging 2h, feed liquid suction filtration dehydration then, 100 ℃ of forced air drying 4h in the filter cake air.The filter cake of drying is placed Muffle furnace, be warming up to 500 ℃, insulation 2h with the speed of 3 ℃/min.After treating that furnace temperature is cooled to room temperature; Get 5g filter cake and 15g natrium citricum and add the 0.2L aqueous solution 150 ℃ of hydro-thermal 4h in agitated reactor, wait solution to be cooled to room temperature after, the dehydration of feed liquid suction filtration; 100 ℃ of forced air drying 4h obtain the exclusive sorbing material of the dye of positive ion of the present invention.Material characterizes with embodiment 1.
The product that obtains is used for the cation dyestuff is pinkish red, the wastewater treatment of anionic dye methyl orange, the result shows: at waste strength is 40mg/L, and the adsorbent consumption is 3.0g/L, adds that pinkish red clearance is 96.2% behind the adsorbent 5min; Can realize Separation of Solid and Liquid easily with magnet.Anionic dye methyl orange there is not suction-operated.
Claims (2)
1. the preparation method of the magnetic mesoporous sorbing material of cationic dyes is characterized in that these method concrete steps are following:
(1) with certain density solubility cobalt salt, the divalent iron salt aqueous solution and after the certain density oxalic acid aqueous solution or the oxalates aqueous solution mix in reactor; Leave standstill heavyization; The mol ratio of said solubility cobalt salt and divalent iron salt is 1:2, and the mol ratio of solubility cobalt salt and divalent iron salt and oxalate denominationby is 1: (1～3), reaction temperature are 20～50 ℃; After leaving standstill heavyization 2～10h, feed liquid is made magnetic mesoporous sorbing material predecessor after dehydration, drying;
(2) the magnetic mesoporous sorbing material predecessor that step (1) is made is calcined under air atmosphere, 1～5 ℃/min of heating rate, and 300～500 ℃ of calcining heats obtain calcined product behind calcining 2～4h;
(3) the calcined product hydro-thermal activation in sodium citrate aqueous solution that step (2) is obtained; Promptly get the exclusive magnetic adsorptive material of the dye of positive ion; The mol ratio of said calcined product and natrium citricum is 1: (3～8); Activation temperature is 80～150 ℃, obtains the magnetic mesoporous sorbing material of said cationic dyes behind hydro-thermal activation 4～10h.
2. the preparation method of the magnetic mesoporous sorbing material of a kind of cationic dyes according to claim 1; It is characterized in that: said solubility cobalt salt is a kind of in cobalt chloride, cobaltous sulfate and the cobalt nitrate; Described divalent iron salt is a kind of in frerrous chloride, ferrous sulfate and the iron ammonium sulfate, and described oxalates is sodium oxalate or potassium oxalate.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103495398A (en) * | 2013-10-22 | 2014-01-08 | 安徽工业大学 | Preparing method and application of carbon-supported magnetic fiber material with one-dimensional core-shell structure |
| CN108393073A (en) * | 2018-02-05 | 2018-08-14 | 大连理工大学 | A kind of preparation method of general magnetic adsorbent and application |
| CN111908513A (en) * | 2020-07-08 | 2020-11-10 | 傅尚真 | Mesomorphic iron oxide material for dye adsorption and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103495398A (en) * | 2013-10-22 | 2014-01-08 | 安徽工业大学 | Preparing method and application of carbon-supported magnetic fiber material with one-dimensional core-shell structure |
| CN103495398B (en) * | 2013-10-22 | 2015-12-02 | 安徽工业大学 | A kind of preparation method carrying carbon magnetic fiber material and application thereof with one-dimensional nucleocapsid structure |
| CN108393073A (en) * | 2018-02-05 | 2018-08-14 | 大连理工大学 | A kind of preparation method of general magnetic adsorbent and application |
| CN108393073B (en) * | 2018-02-05 | 2020-02-18 | 大连理工大学 | Preparation method and application of general magnetic adsorbent |
| CN111908513A (en) * | 2020-07-08 | 2020-11-10 | 傅尚真 | Mesomorphic iron oxide material for dye adsorption and preparation method thereof |
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