CN103566971B - A kind of preparation method of metal complex catalysts of microcapsules load - Google Patents
A kind of preparation method of metal complex catalysts of microcapsules load Download PDFInfo
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- CN103566971B CN103566971B CN201310548220.3A CN201310548220A CN103566971B CN 103566971 B CN103566971 B CN 103566971B CN 201310548220 A CN201310548220 A CN 201310548220A CN 103566971 B CN103566971 B CN 103566971B
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Abstract
The present invention relates to a kind of preparation method of metal complex catalysts of microcapsules load, preparation method is: multiple emulsion-solvent evaporation, emulsion-crosslinking method and intra-liquid desiccation method.Use the metal complex catalysts after load of the present invention and hydrogen peroxide catalytic oxidation process to contain the waste water of dyestuff, percent of decolourization is high, and catalytic effect is obvious, and can be recycled.Use technical scheme of the present invention, be conducive to the fixing of catalytic active component, improve the stability of catalyst, simple to operate, be applicable to the catalytic oxidation treatment of waste water containing dye, catalyst can repeatedly recycle, and reduces processing cost.
Description
Technical field
The invention belongs to the preparation field of catalyst material, the preparation method of the metal complex catalysts of particularly a kind of microcapsules load.
Background technology
The Control and treatment of environmental pollution is facing mankind and the significant problem needing solution badly, and increasing of industry and domestic refuse, drastically influence the ecological environment that the mankind depend on for existence.Research for these Organic Waste Water Treatments has caused extensive concern both domestic and external.Metal complex is used for as catalyst the focus that oxidative degradation organic pollution is recent domestic scholar's research.
At document [SorokinA, Seri, JL, MeunierB.Science, 1995,268:1163-1166] and [SorokinA, Suzzoni-DezardSD, MeunierB.JAmChemSoc, 1996,118 (31): 7410-7411] in, BernardMeunier etc. utilize water miscible sulfonated phthalocyanine FePcS successfully to degrade 2 in water, and 4-chlorophenol, obtains quite high mineralization rate.Reviews [Fan Zhiyun, Li Aimin, Wu Lin, principality China etc. modern chemical industry .2006,26 (10): 20-24]] in also have the report using it for catalyze and degrade organic pollutants.Document [Shul ' pinGB, KozlovYN, KholuiskayaSN, PlievaMI.JournalofMolecularCatalysisA:Chemical299 (2009) 77-87] in the catalyzing oxidizing degrading that the catalyst of ring polyamines structure is used for dye, rhodamine such as GeorgiyB.Shul ' pin achieve good effect.
But a lot of metal complex catalysts is also unstable, very easily occur to assemble and inactivation in water, thus, loaded catalyst also more and more receives the concern of people.The major advantage of supported catalyst has: (1) post-reaction treatment is convenient, can be isolated by simple filtration; (2) the conventional expensive reagent/catalyst of load can be reclaimed and repeat to make; (3) stability of catalyst is improved; (4) ion of toxic reagent or heavy metal is fixed on the carrier of reaction, can reduce them and be lost to that the solution of reaction is medium carries out pollution control.Supported method has a lot, and the technological means by microencapsulation can prepare the metal complex catalysts of microcapsules load, thus improves its stability, is convenient to recycle.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of metal complex catalysts of microcapsules load, and this catalyst percent of decolourization is high, catalytic effect obvious, can be recycled.
The preparation method of the metal complex catalysts of a kind of microcapsules load of the present invention, comprising: emulsion evaporation, emulsion-crosslinking method or intra-liquid desiccation method;
Wherein the concrete steps of emulsion evaporation are: be dissolved or mixed in by metal complex catalysts in water, obtain aqueous phase; Encapsulating material is dissolved in volatilization class organic solvent, obtains oil phase; Aqueous phase and oil phase are mixed in the mode of emulsification, obtains water-in-oil emulsion, then add in water (i.e. outer aqueous phase), dispersion and emulsion, obtain W/O/W emulsion, volatilization, centrifugation, washing, drying, obtain the metal complex catalysts after microcapsules load; Wherein, the volume ratio of oil phase and aqueous phase is (1-100): 1, and the concentration range of catalyst in water is 0.001-10wt%, and the concentration range of encapsulating material in oil phase is 1-10wt%, and the volume ratio of outer aqueous phase and water-in-oil emulsion is (100-1): 1;
The concrete steps of emulsion-crosslinking method are: be dissolved in by encapsulating material in water, and then mixing or dissolution of metals composition catalyst, obtain aqueous phase; Aqueous phase is mixed mutually with the hydrophobic of molten condition, emulsification, obtains water-in-oil emulsion, then water-in-oil emulsion is cooled to and adds crosslinking agent and carry out crosslinking curing, filter, washing, cold dry, obtain the metal complex catalysts after microcapsules load; Wherein, the concentration range of metal complex in water is 0.001-10wt%, the concentration range of encapsulating material in water is 1-10wt%, the mass ratio of encapsulating material and metal complex is (1-1000): 1, the volume ratio of hydrophobic phase and aqueous phase is (1-1000): 1, and the mass ratio of crosslinking agent and encapsulating material is (0.001-1): 1;
The concrete steps of intra-liquid desiccation method are: be dissolved in by encapsulating material in volatilization class organic solvent, then dissolve or hybrid metal composition catalyst, obtain oil phase; Oil phase is mixed mutually with the hydrophobic of molten condition, emulsification, obtains oily bag fat liquor, then volatilize, filter, wash, dry, obtain the metal complex catalysts after microcapsules load; Wherein, metal complex concentration range is in organic solvent 0.001-10wt%, encapsulating material concentration range is in organic solvent 1-10wt%, the mass ratio of encapsulating material and metal complex is (1-1000): 1, and the hydrophobic phase of molten state and the volume ratio of oil phase are (1-1000): 1.
Encapsulating material in described emulsion evaporation is one or more in PLA, polystyrene, polymethyl methacrylate, methylcellulose, ethyl cellulose, carboxymethyl cellulose, preferred, ethyl; Volatilization class organic solvent is chloroform, toluene, ethyl acetate or carrene.
The mode of described volatilization comprise normal temperature leave standstill, heat up stir, vacuum revolves steaming or low temperature slowly volatilizees; Dry mode comprises that nature dries, high temperature drying or freeze drying, preferably freeze drying.
Encapsulating material in described emulsion-crosslinking method is one or more in shitosan, sodium alginate, gelatin, Arabic gum, preferred gelatin.
Described hydrophobic be one or more in animal oil, vegetable oil, animal wax, vegetable wax, mineral tallow, synthetic wax, natural synthetic resin mutually, preferred paraffin.
Described crosslinking agent is formaldehyde or glutaraldehyde.
In described intra-liquid desiccation method, volatile organic solvent is one or more in methyl alcohol, ethanol, acetone, carrene.
The metal complex catalysts of gained microcapsules load is as waste water from dyestuff oxidation catalyst.
beneficial effect
(1) metal complex catalysts after working load of the present invention and hydrogen peroxide catalytic oxidation process contain the waste water of dyestuff, and percent of decolourization is high, and catalytic effect is obvious, and can be recycled;
(2) use technical scheme of the present invention, be conducive to the fixing of catalytic active component, improve the stability of catalyst, simple to operate, be applicable to the catalytic oxidation treatment of waste water containing dye, catalyst can repeatedly recycle, and reduces processing cost.
Accompanying drawing explanation
The light microscope of Fig. 1 Ethylcellulose Microspheres supported metal complex catalyst;
The light microscope of Fig. 2 gelatine microsphere supported metal complex catalyst;
The ESEM of Fig. 3 Ethylcellulose Microspheres supported metal complex catalyst;
The ESEM of Fig. 4 gelatine microsphere supported metal complex catalyst;
The recycling property of Fig. 5 micro-ball load metal complex catalysts.
Detailed description of the invention
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
Multiple emulsion-solvent evaporation prepares microcapsules supported metal complex catalyst: by 30mg ring polyamines manganese complex 6ml deionized water dissolving, obtain the core aqueous solution.Fully dissolve 3g ethyl cellulose with 50ml carrene, obtain wall material solution.By the dichloromethane solution of the core aqueous solution and wall material with the rotating speed stirring and emulsifying of 4000r/m, pour into rapidly in the outer aqueous phase solution of preprepared 500ml, and under the rotating speed of 400r/m continuous stirring and emulsifying 60min, environment temperature is maintained about 30 DEG C subsequently, continue to stir volatilization to ensure that carrene wherein volatilizees completely.The centrifugal mode of suspension will obtained afterwards, collects product with the rotating speed of 5000r/m, and spends deionized water, freeze drying.Products obtained therefrom is labeled as 1# catalyst temporarily.
Embodiment 2
Emulsion-crosslinking method prepares microcapsules supported metal complex catalyst: 1g gelatin 10ml deionized water dissolving is complete, then is dissolved wherein by 20mg ring polyamines manganese complex.Mixture aqueous solution obtained above is emulsified in 100ml paraffin at the speed of agitator of 400r/m, and the emulsion after emulsification is evenly carried out crosslinking Treatment with glutaraldehyde in ice bath, is leached by the product after solidification afterwards, washing is dry.Products obtained therefrom is labeled as 2# catalyst temporarily.
Embodiment 3
Intra-liquid desiccation method prepares microcapsules supported metal complex catalyst: 30mg ring polyamines manganese complex and 2g ethyl cellulose 20ml acetone are fully dissolved, and join in 100ml paraffin.400r/m emulsification is stirred, and the emulsion obtained is continued to stir at 40 DEG C afterwards, until fully volatilized by acetone solvent, leached by the product after solidification, washing is dry.Products obtained therefrom is labeled as 3# catalyst temporarily.
Embodiment 4
With the microcapsules supported metal complex catalyst that embodiment 1-3 is obtained, the catalytic oxidation activity be respectively used to containing the waste water from dyestuff of reactive blue, acid orange, reactive scarlet is investigated: the aqueous dye solutions of deionized water preparation 100mg/L, as catalytic oxidation use target waste water.Hydrogen peroxide with 30%, as oxidant, joins in dye solution.With the new sodium hydrate regulator solution pH prepared to about 10.Add microcapsules supported metal complex catalyst (1# ~ 3#) prepared by above-described embodiment 1-3.40 DEG C of water bath with thermostatic control process 60min.With the oxidative decoloration rate of each dyestuff for evaluation index, investigate the catalytic decolorization effect of above-mentioned microcapsules supported metal complex catalyst.Add one group of blank's test simultaneously, wherein do not add any catalyst.Investigation result is as shown in table 1.
Table 1 microcapsules supported metal complex catalytic activity investigates result
| Group number | Blank group | 1# catalyst | 2# catalyst | 3# catalyst |
| Reactive blue percent of decolourization (%) | 7 | 95 | 98 | 90 |
| Acid orange percent of decolourization (%) | 3 | 94 | 99 | 91 |
| Reactive scarlet percent of decolourization (%) | 5 | 92 | 97 | 92 |
As shown in result in table 1, dye solution hydrogen peroxide 40 DEG C of oxidation processes 60min, be difficult to be oxidized decolorizing effect under the condition not adding catalyst, and the metal complex catalysts rear decoloring rate adding microcapsules load is all more than 90%, illustrate that the metal complex catalysts after the microcapsules load prepared in the present invention has good catalytic activity, can be used for the catalytic oxidation treatment of industrial wastewater.
Embodiment 5
This embodiment relate to the metal complex catalysts of microcapsules load is circulated after recycling:
The metal complex catalysts of the microcapsules load in dye solution after catalytic oxidation is directly leached from the dye solution after oxidative decoloration, after deionized water washing, be directly used in the catalytic oxidation desolventing technology of next round waste water from dyestuff, record the oxidative decoloration rate of dyestuff, thus investigate the metal complex catalysts of microcapsules loads recycle performance.
Be specially: the reactive blue dye aqueous solution of deionized water preparation 100mg/L, in this, as catalytic oxidation use target waste water.Hydrogen peroxide with 30%, as oxidant, joins in dye solution.With the new sodium hydrate regulator solution pH prepared to about 10.Add the catalyst of above-mentioned microcapsules load.40 DEG C of water bath with thermostatic control process 60min, leach microcapsules wherein, the oxidative decoloration of next group reactive blue of catalysis is used further to after deionized water washing, with the oxidative decoloration rate of reactive blue for evaluation index, the metal complex catalysts investigating above-mentioned microcapsules load takes turns the catalytic oxidation decolorizing effect in reaction at each.
Actual result is shown in accompanying drawing 5, result from figure, and the metal complex catalysts of microcapsules load prepared by the present invention has well recycling property, thus can reduce production cost to a certain extent.
The present invention is not limited only to foregoing description, not departing from the scope described in the claims in the present invention, can be changed by different way or improve.
Claims (8)
1. a preparation method for the metal complex catalysts of microcapsules load, is characterized in that: preparation method is emulsion evaporation,
Wherein the concrete steps of emulsion evaporation are: be dissolved or mixed in by metal complex catalysts in water, obtain aqueous phase; Encapsulating material is dissolved in volatilization class organic solvent, obtains oil phase; Aqueous phase and oil phase are mixed in the mode of emulsification, obtains water-in-oil emulsion, be then added to the water, dispersion and emulsion, obtain W/O/W emulsion, volatilization, centrifugation, washing, drying, obtain the metal complex catalysts after microcapsules load; Wherein, the volume ratio of oil phase and aqueous phase is (1-100): 1, the concentration range of catalyst in water is 0.001-10wt%, and the concentration range of encapsulating material in oil phase is 1-10wt%, and the volume ratio of outer aqueous phase and water-in-oil emulsion is (100-1): 1; Encapsulating material wherein in emulsion evaporation is one or more in PLA, polystyrene, polymethyl methacrylate, methylcellulose, ethyl cellulose, carboxymethyl cellulose; Volatilization class organic solvent is chloroform, toluene, ethyl acetate or carrene.
2. the preparation method of the metal complex catalysts of a microcapsules load, it is characterized in that: preparation method is emulsion-crosslinking method, wherein the concrete steps of emulsion-crosslinking method are: be dissolved in by encapsulating material in water, and then mixing or dissolution of metals composition catalyst, obtain aqueous phase; Aqueous phase is mixed mutually with the hydrophobic of molten condition, emulsification, obtains water-in-oil emulsion, then water-in-oil emulsion is lowered the temperature and add crosslinking agent and carry out crosslinking curing, filter, washing, cold dry, obtain the metal complex catalysts after microcapsules load; Wherein, the concentration range of metal complex in water is 0.001-10wt%, the concentration range of encapsulating material in water is 1-10wt%, the mass ratio of encapsulating material and metal complex is (1-1000): 1, the volume ratio of hydrophobic phase and aqueous phase is (1-1000): 1, and the mass ratio of crosslinking agent and encapsulating material is (0.001-1): 1; Encapsulating material wherein in emulsion-crosslinking method is one or more in shitosan, sodium alginate, gelatin, Arabic gum.
3. the preparation method of the metal complex catalysts of a microcapsules load, it is characterized in that: preparation method is intra-liquid desiccation method, wherein the concrete steps of intra-liquid desiccation method are: be dissolved in by encapsulating material in volatilization class organic solvent, then dissolve or hybrid metal composition catalyst, obtain oil phase; Oil phase is mixed mutually with the hydrophobic of molten condition, emulsification, obtains oily bag fat liquor, then volatilize, filter, wash, dry, obtain the metal complex catalysts after microcapsules load; Wherein, metal complex concentration range is in organic solvent 0.001-10wt%, encapsulating material concentration range is in organic solvent 1-10wt%, the mass ratio of encapsulating material and metal complex is (1-1000): 1, and the hydrophobic phase of molten state and the volume ratio of oil phase are (1-1000): 1.
4. the preparation method of the metal complex catalysts of a kind of microcapsules load according to claim 1, is characterized in that: the mode of described volatilization comprise normal temperature leave standstill, heat up stir, vacuum revolves steaming or low temperature slowly volatilizees; Dry mode comprises that nature dries, high temperature drying or freeze drying.
5. the preparation method of the metal complex catalysts of a kind of microcapsules load according to Claims 2 or 3, is characterized in that: described hydrophobic be animal oil, vegetable oil, animal wax, vegetable wax, mineral tallow, synthetic wax, one or more in natural synthetic resin mutually.
6. the preparation method of the metal complex catalysts of a kind of microcapsules load according to claim 2, is characterized in that: described crosslinking agent is formaldehyde or glutaraldehyde.
7. the preparation method of the metal complex catalysts of a kind of microcapsules load according to claim 3, is characterized in that: in described intra-liquid desiccation method, volatile organic solvent is one or more in methyl alcohol, ethanol, acetone, carrene.
8., according to the preparation method of the metal complex catalysts of the arbitrary described microcapsules load of claim 1-3, it is characterized in that: the metal complex catalysts of the microcapsules load of gained is as waste water from dyestuff oxidation catalyst.
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| CN112079980B (en) * | 2020-09-10 | 2022-05-03 | 浙江华峰合成树脂有限公司 | Polyurethane composite catalyst, solvent-free polyurethane resin thereof and preparation method |
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