CN101367562B - Method for degradation of organochloride - Google Patents
Method for degradation of organochloride Download PDFInfo
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- CN101367562B CN101367562B CN2008100702329A CN200810070232A CN101367562B CN 101367562 B CN101367562 B CN 101367562B CN 2008100702329 A CN2008100702329 A CN 2008100702329A CN 200810070232 A CN200810070232 A CN 200810070232A CN 101367562 B CN101367562 B CN 101367562B
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- hollow glass
- glass micropearl
- waste water
- alloy layer
- organic chloride
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Abstract
The invention relates to a method for degrading the chloride, which comprises the following steps: firstly the surface of the hollow glass micro balloon is loaded with the iron and nickel dual-metal particles so as to modify the surface of the hollow glass micro balloon in liquid-phaseelectroless plating way; secondly, the modified hollow glass micro balloon is adopted as the absorption agent, the restoration agent and the catalyst to degrade the organic chloride. On the one hand, the problem of the load of the catalyst (Fe-Ni) is resolved; on the other hand, the surface area of the catalyst is enlarged, so that the active center of the reaction is increased; moreover, after heating and promoting with the micro wave in the reaction, a plurality of heat points can be generated on the surface of the hollow glass micro balloon, thereby greatly improving the absorption efficiency of the micro-wave energy. Under the cooperative effect of the absorption of the modified hollow glass micro balloon and the inducement of the micro wave, the degradation of the organic chloride is more efficient and more thorough. The method is simple to be operated, and is free from generating the toxic intermediate bodies, and has good effect to degrade the organic chloride, and is a good method for processing the organic chloride waste water.
Description
Technical field
The present invention relates to method that organic chloride is degraded.
Background technology
Organic chloride comprises chloroparaffin, chloro-alkenes, chlorination aromatic hydrocarbon and organochlorine insecticide etc.Along with the organic chemistry industrial expansion, it is used widely at aspects such as medicine, process hides, electronics and agricultural chemicals, causes a large amount of chloride compounds and the intermediate product in the building-up process or byproduct to be discharged in the environment in large quantities.Some organic chloride in the environment can consume the ozone in the atmospheric layer, and some then can endanger people's central nervous system, brings out cancer.The all toxic and difficult degradation of nearly all chlorinated aromatic hydrocarbons and derivative thereof, wherein quite a few is listed in U.S. EPA environment priority pollutants.This pollutant chemical property is stable, will cause long-term threat to the mankind and ecotope thereof in case enter environment.Therefore, in recent years, the degradation treatment technology of organic chloride has caused extensive concern both domestic and external.
At present, handling the most frequently used method of organic chloride waste liquid is to burn, but often follows the incomplete combustion product thus.Burning as tetracol phenixin can produce the material that other thermostabilitys are higher, toxicity is bigger, as Perchlorobenzene.And incineration ashes hydrogenchloride also need reclaim and do suitable processing.In addition, organic chloride, especially many chloros pollutent are difficult to as Lewis acid (electron acceptor(EA)) effectively handle with high-level oxidation technology (AOPs) usually.The degradation method of organic chloride also has biological process, the method for chemical method and physics usually.Wherein, the physical method effect is bad, and biological method is too loaded down with trivial details and wayward again, and what use always in the chemical process is with Zero-valent Iron deoxidization, degradation organic chloride.But common metallic iron, along with the carrying out of reaction, its surface forms inert layer or metal hydroxides and reactive activity is reduced, and produces a large amount of deleterious intermediates.
Summary of the invention
The objective of the invention is,, provide a kind of method that can not produce the degradation of organochloride that poisonous intermediate, operation are simple relatively, efficient is higher relatively at the deficiencies in the prior art.
For reaching goal of the invention, a kind of like this method of degradation of organochloride is provided, this method is with sorbent material organic chloride contained in the waste water to be adsorbed.Its improvements are, the sorbent material among the present invention is the hollow glass micropearl that its coating surface has the Fe-Ni alloy layer, and this method comprises the steps:
A, the order that hollow glass micropearl is cleaned after according to oil removing cleaning, alligatoring, activation, reduction, dispergation and dispergation are carried out pre-treatment;
B, the hollow glass micropearl surface of having cleaned behind dispergation with liquid phase chemical plating method plating Fe-Ni alloy layer, then, are cleaned, drying; In the Fe-Ni alloy layer, Fe: Ni=2: 1～3: 1;
C, with plating the Fe-Ni alloy layer hollow glass micropearl with contain organic muriatic waste water, the quality according to 1%～1.2% is regulated pH value to 4.5～5.5 than thorough mixing; Then, under microwave action, stir 10～30min, to allow plating that organic chloride in the hollow glass micropearl absorption waste water of Fe-Ni alloy layer is arranged; Wherein, microwave frequency is 2000～2800MHz, and power is 600～1000W;
D, filtering separation have been adsorbed the hollow glass micropearl of organic chloride and treated waste water;
E, to the isolated hollow glass micropearl that adsorbs organic chloride, again according to the order of step a carry out manipulation of regeneration, to recycle.
As can be seen, the sorbent material hollow glass micropearl among the present invention just uses afterwards at its coating surface Fe-Ni alloy layer (promptly to its modification) from scheme.Replace the Zero-valent Iron degradation of organochloride with the hollow glass micropearl after the modification following advantage is arranged: (1) has increased surface-area; (2) increased surface reaction; (3) reduce byproduct of reaction.With the method for modifying of bimetal (Fe-Ni) particle load on hollow glass micropearl, also solved the loading problem of this bimetal (Fe-Ni) catalyzer simultaneously, catalyzer exists with solid-state, and is easy with separating of waste water; And the adsorptive power of carrier (hollow glass micropearl) provides the concentration environment for catalyzed reaction, improves speed of reaction; Also increased the surface-area of catalyzer in addition, the reactive activity center is increased; The bimetal on hollow glass micropearl surface (Fe-Ni) particle has the ability of very strong absorption microwave, realizes the conversion of micro-wave energy.Microwave radiation has efficient reacting by heating system as a kind of new technology of water treatment, quickens the effect of thermo-negative reaction.The modification hollow glass micropearl has very strong receptivity as a kind of absorbing material to microwave, and the hollow glass micropearl surface can produce many " focuses " when microwave radiation.The temperature of these " focuses " is more much higher than other positions, the carrying out of impelling catalyzed reaction.In a word, hollow glass micropearl not only has adsorption after the modification, but also has possessed catalysis, reductive action.The inventive method does not produce poisonous intermediate, operates the higher relatively characteristics of efficient simple relatively, degradation of organochloride compared with prior art.
Below in conjunction with embodiment, the present invention is further illustrated.
Embodiment
A kind of method of degradation of organochloride, this method are with sorbent material organic chloride contained in the waste water to be adsorbed.In the present invention, this sorbent material is the hollow glass micropearl that its coating surface has the Fe-Ni alloy layer.This method comprises the steps:
One, hollow glass micropearl being carried out modification handles
A, the order that hollow glass micropearl is cleaned after according to oil removing cleaning, alligatoring, activation, reduction, dispergation and dispergation are carried out pre-treatment;
B, the hollow glass micropearl surface of having cleaned behind dispergation with liquid phase chemical plating method plating Fe-Ni alloy layer, then, are cleaned, drying; In the Fe-Ni alloy layer, Fe: Ni=2: 1～3: 1;
Two, with the hollow glass micropearl degradation of organochloride after the modification
C, with plating the Fe-Ni alloy layer hollow glass micropearl with contain organic muriatic waste water, the quality according to 1%～1.2% is regulated pH value to 4.5～5.5 than thorough mixing; Then, under microwave action, stir 10～30min, to allow plating that organic chloride in the hollow glass micropearl absorption waste water of Fe-Ni alloy layer is arranged; Wherein, microwave frequency is 2000～2800MHz, and power is 600～1000W;
D, filtering separation have been adsorbed the hollow glass micropearl of organic chloride and treated waste water;
Three, reclaim, handle again, to recycle hollow glass micropearl
E, to the isolated hollow glass micropearl that adsorbs organic chloride, again according to the order of step a carry out manipulation of regeneration, to recycle.
Indubitable, also should carry out necessary chemical examination to treated waste water.According to result of laboratory test, perhaps directly recycle or the middle water of making other purposes in addition use or further handle back recirculation and use or do his in addition and use.
Those skilled in the art know that, the mass ratio of the ratio of above-mentioned Fe-Ni alloy, hollow glass micropearl and organic chloride and pH value, microwave frequency and power thereof, these processing parameters of churning time, when actually operating, should in the scope of these processing parameters, adjust according to the difference of hollow glass micropearl, the particular cases such as concentration of organic chloride.In most of the cases, get:
Fe∶Ni＝3∶1
Hollow glass micropearl is 1% with the mass ratio that contains organic muriatic waste water, and its pH value is 5 (in this embodiment, regulating the pH value with sulfuric acid and sodium hydroxide)
Microwave frequency is 2450MHz, and power is 800W, and churning time is 10min.
Further, in the step a of this embodiment, the activation solution that hollow glass micropearl is carried out activation treatment contains Palladous chloride (PdCl
2), tin protochloride (SnCl
2), hydrochloric acid (HCl), in every L activation solution: Palladous chloride (PdCl
2) 0.09g～0.11g, tin protochloride (SnCl
2) 13.5g～16.5g, hydrochloric acid (HCl) 180mL～220mL, all the other are water (the proportioning example sees Table 1); Hollow glass micropearl after the activation is carried out the glue of separating that dispergation handles contain hydrochloric acid (HCl), ionic liquid, every L separates in the glue: hydrochloric acid (HCl) 90mL～110mL, ionic liquid 45mL～55mL, all the other are water (the proportioning example sees Table 2).
The every L activation solution of table 1 proportioning example
The every L of table 2 separates glue proportioning example
Say that further in the step b of this embodiment, chemical plating fluid is main salt with single nickel salt, ferrous sulfate, inferior sodium phosphate is a reductive agent, and Seignette salt is a complexing agent, in every L chemical plating fluid: single nickel salt (NiSO
4) 7g～9g, ferrous sulfate (FeSO
4) 20g～23g, inferior sodium phosphate (NaH
2PO
2) 34～36, Seignette salt (KNaC
6H
2O
6) 82g～84g, sodium hydroxide (NaOH) 38g～40g, surplus is a water.Temperature of reaction is 70 ℃～80 ℃, reaction times 60min～65min, stir speed (S.S.) 180r/min～250r/min (proportioning and corresponding process parameters example see Table 3).
The every 1L chemical plating fluid of table 3 proportioning example
Disclose so far, those skilled in the art can basic comprehension.For helping those skilled in the art to understand better and realizing the present invention, existing checking of the present invention is described below.
The checking content:
Measure and calculate the chlorion theoretical concentration in the waste water before the degraded (because the chlorine in the waste water is not that form with chlorion exists before the degraded, just can produce chlorion after the degraded), the massfraction of chlorine element in the concentration * organic chloride of organic chloride in the preceding waste water of the chlorion theoretical concentration=degraded before this degraded in the waste water;
Measure the chlorine ion concentration in the waste water of degraded back---with the chloride ion content in the chloride ion-selective electrode mensuration waste water.
Measure according to following formula then and calculate dechlorination rate:
Chlorion theoretical concentration * 100% checking result such as following table before chlorine ion concentration/degraded in dechlorination rate (%)=degraded back waste water in the waste water:
| Numbering | The organic chloride species | B | Microwave power (W) | The microwave time (min) | Chlorion theoretical concentration (mg.L before the degraded in the waste water -1) | Concentration (the mg.L of chlorion in the waste water of degraded back -1) | pH | Dechlorination rate (%) |
| One | Trichloromethane | 1.0 | 700 | 10 | 713 | 671 | 4.5 | 94.1 |
| Two | Tetracol phenixin | 1.1 | 800 | 15 | 830 | 807 | 5 | 97.2 |
| Three | Tetrachloroethane | 1.2 | 900 | 10 | 845 | 828 | 5 | 98.0 |
| Four | Trieline | 1.0 | 800 | 15 | 729 | 717 | 5.5 | 98.4 |
| Five | Chlorophenic acid | 1.1 | 900 | 10 | 276 | 273 | 5 | 98.9 |
In the last table: B---hollow glass micropearl and the mass ratio (%) that contains organic muriatic waste water
As can be seen from the above table: appropriateness increases microwave power, helps to improve dechlorination rate.
Claims (3)
1. the method for a degradation of organochloride, this method is with sorbent material organic chloride contained in the waste water to be adsorbed, and it is characterized in that, and described sorbent material is the hollow glass micropearl that its coating surface has the Fe-Ni alloy layer, and this method comprises the steps:
A, the order that hollow glass micropearl is cleaned after according to oil removing cleaning, alligatoring, activation, reduction, dispergation and dispergation are carried out pre-treatment;
B, the hollow glass micropearl surface of having cleaned behind dispergation with liquid phase chemical plating method plating Fe-Ni alloy layer, then, are cleaned, drying; In the Fe-Ni alloy layer, Fe: Ni=2: 1～3: 1;
C, with plating the Fe-Ni alloy layer hollow glass micropearl with contain organic muriatic waste water, the quality according to 1%～1.2% is regulated pH value to 4.5～5.5 than thorough mixing; Then, under microwave action, stir 10～30min, to allow plating that organic chloride in the hollow glass micropearl absorption waste water of Fe-Ni alloy layer is arranged; Wherein, microwave frequency is 2000～2800MHz, and power is 600～1000W;
D, filtering separation have been adsorbed the hollow glass micropearl of organic chloride and treated waste water;
E, to the isolated hollow glass micropearl that adsorbs organic chloride, again according to the order of step a carry out manipulation of regeneration, to recycle.
2. according to the method for the described degradation of organochloride of claim 1, it is characterized in that: in step b, chemical plating fluid is main salt with single nickel salt, ferrous sulfate, inferior sodium phosphate is a reductive agent, Seignette salt is a complexing agent, in every L chemical plating fluid: single nickel salt 7g～9g, ferrous sulfate 20g～23g, inferior sodium phosphate 34g～36g, Seignette salt 82g～84g, sodium hydroxide 38g～40g, all the other are water, temperature of reaction is 70 ℃～80 ℃, reaction times 60min～65min, stir speed (S.S.) 180r/min～250r/min.
3. according to the method for claim 1 or 2 described degradation of organochloride, it is characterized in that: in the described Fe-Ni alloy layer of step b, Fe: Ni=3: 1; In described step c, plating the hollow glass micropearl of Fe-Ni alloy layer with to contain organic muriatic waste water blended mass ratio be 1%, its pH value is 5, microwave frequency is 2450MHz, power is 800W, churning time is 10min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100702329A CN101367562B (en) | 2008-09-05 | 2008-09-05 | Method for degradation of organochloride |
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|---|---|---|---|
| CN2008100702329A CN101367562B (en) | 2008-09-05 | 2008-09-05 | Method for degradation of organochloride |
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|---|---|
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| CN101367562B true CN101367562B (en) | 2010-09-01 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101575150B (en) * | 2009-06-10 | 2012-01-04 | 重庆大学 | Method for degrading chloro-organic waste water by using double-metals reinforced by microwaves |
| CN102120123A (en) * | 2011-02-15 | 2011-07-13 | 中国科学院过程工程研究所 | Method for absorbing chlorohydrocarbons by ionic liquid |
| CN109111719B (en) * | 2017-06-26 | 2022-12-13 | 洛阳尖端技术研究院 | Wave-absorbing material and preparation method thereof |
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