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CN102295341A - Method for treating chlorine-containing organic waste water by heterogeneous phase Fenton-like reaction - Google Patents

Method for treating chlorine-containing organic waste water by heterogeneous phase Fenton-like reaction Download PDF

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CN102295341A
CN102295341A CN2011101581855A CN201110158185A CN102295341A CN 102295341 A CN102295341 A CN 102295341A CN 2011101581855 A CN2011101581855 A CN 2011101581855A CN 201110158185 A CN201110158185 A CN 201110158185A CN 102295341 A CN102295341 A CN 102295341A
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王建龙
徐乐瑾
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Tsinghua University
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Abstract

The invention discloses a method for treating chlorine-containing organic waste water by a heterogeneous phase Fenton-like reaction, which belongs to the technical field of environment protection. The method adopts nanometer FeO, nanometer Fe3O4 or a mixture of nanometer FeO/Fe3O4 as a Fenton-like catalyst, and allows chlorine-containing organic waste water to react in the presence of both the Fenton-like catalyst and H2O2 so as to degrade chloro-substituted organic matter in the waste water. The invention has simple equipment, convenient operations, easily available reagents, can efficiently remove chlorine-containing organic matter in waste water within a wide pH range (Ph 2.0-6.3), and has great application prospects.

Description

The method of the chloride organic waste water of a kind of heterogeneous Fenton-like reaction treatment
Technical field
The invention belongs to environmental protection technical field, be specifically related to the method for the chloride organic waste water of a kind of heterogeneous Fenton-like reaction treatment.
Background technology
Chlorinatedorganic comprises hydrochloric ether, chlorination aromatic hydrocarbon, organochlorine insecticide etc., is widely used in industries such as printing and dyeing, papermaking, dry-cleaning, metal parts processing, electronics manufacturing, organic pesticide.Because of its numerous sources, in surface water, underground water and soil, can detect their existence now.Chloride organic waste water toxicity is big, and difficult for biological degradation has " three cause effect ", and ecotope and human health have been caused direct destruction and potential threat.Therefore, research treatment process and technology economic, efficient, non-secondary pollution has great importance.
Traditional water treatment method has as absorption, flocculation, precipitation, biological process etc. that efficient is low, cost is high, easily produce limitation such as secondary pollution.In recent years, the high-level oxidation technology in the chemical method becomes the focus that people pay close attention to gradually, and it utilizes the very strong hydroxyl radical free radical of oxidisability (OH) to come organic pollutant in the oxygenolysis water.Wherein, Fenton reagent (being the combination of ferrous salt and the hydrogen peroxide) research that is used for removing the water organic pollutant is on the increase.The action principle of this method is based on hydrogen peroxide (H 2O 2) and the homogeneous phase metal ion catalyst between electric transmission, and then produce can degradation of organic substances free radical, the most frequently used catalyzer is a ferrous ion.Compare with other advanced oxidation processes, Fenton reagent method has rapidly and efficiently, operating process is simple, need not complex apparatus, to follow-up processing toxicological harmless effect and advantage such as environmentally friendly, be applied to gradually in the waste water treatment engineerings such as pulping and paper-making, dyestuff, agricultural chemicals.But traditional Fenton reagent method still exists a lot of deficiencies in actual applications, as H 2O 2Utilization ratio is not high; The optimal ph of reaction is confined to 2～4, needs to regulate the pH value before the reaction and after the reaction; After reaction is finished, need with methods such as precipitations the iron ion in the solution to be separated, the expense of aftertreatment is more high.
For overcoming many deficiencies of homogeneous phase Fenton reaction, a lot of scholars study heterogeneous Fenton-like system.It is that solid catalyst replaces homogeneous ferrous salt and hydrogen peroxide or oxygen reaction that so-called heterogeneous Fenton-like oxidation system is to use heterogeneous iron; In these systems,, the solid iron catalyzer come catalyzing hydrogen peroxide to excite the Fenton reaction as homogeneous catalyst thereby can discharging ferrous ion from the surface.Heterogeneous Fenton-like reaction can be carried out in the pH of broad scope, have rate of oxidation height, catalyzer source wide, be easy to recycle and reaction process in can not produce advantage such as a large amount of ferriferous oxide precipitations, provide wide prospect for handling poisonous and harmful difficult for biological degradation organic waste water.
Summary of the invention
The objective of the invention is to solve the shortcoming of prior art, provide a kind of equipment simple, easy to operate, can be in the pH of broad scope (pH 2.0～6.3) remove the heterogeneous Fenton-like oxidation style of chlorinated organics in the waste water efficiently.
The method of the chloride organic waste water of a kind of heterogeneous Fenton-like reaction treatment, this method is with nanometer Fe 0, nanometer Fe 3O 4Or nanometer Fe 0/ Fe 3O 4Mixture is the Fenton-like catalyzer, at above-mentioned Fenton-like catalyzer and H 2O 2Exist simultaneously down and react with chloride organic waste water, with the degraded of the chlorinatedorganic in the waste water, wherein, nanometer Fe 0/ Fe 3O 4Mixture refers to nano zero valence iron (Fe 0) and magnetic Nano Z 250 (Fe 3O 4) mixture.
Nanometer Fe 0/ Fe 3O 4Fe in the mixture 0With Fe 3O 4The optimization quality be (0.5～5) than scope: 1.
The pH value of described chloride organic waste water is 2.0～6.3.
When chloride organic waste water concentration is 80～160mg/L, nanometer Fe 0, nanometer Fe 3O 4Or nanometer Fe 0/ Fe 3O 4The optimization consumption of mixture is 0.5～1.0g/L, H 2O 2The optimization consumption be 3～30mM.
Described nanometer Fe 0Form be the rule spheroidal particle, particle diameter is 80～150nm.Nanometer Fe 0The preparation method be: in reaction vessel, add certain density FeSO in advance 47H 2O solution stirs and feeds argon gas and make it to be in anaerobic state, with certain density KBH 4Solution splashes in the reaction vessel with certain speed, makes its reaction generate nano-iron particle, KBH 4Solution and FeSO 47H 2The volume ratio scope of O solution is 1: 1～2.5: 1, and the concentration ratio scope is 5: 1～8: 1, guarantees BH 4 -Excessive; Its reaction principle is Fe (H 2O) 6 2++ 2BH 4 -→ Fe 0↓+2B (OH) 3+ 7H 2Individual; Blast argon gas in the reaction process and keep being reflected under the anaerobic state carrying out, the micro-bubble that aeration produces adheres to nuclear and prevents nanometer Fe as iron atom 0The reunion of particle keeps stirring to make solution be in the uniform mixing state.Behind reaction 1～2h, with synthetic nano-iron particle precipitation, with promptly making nanometer Fe after deionized water wash and the vacuum-drying 0
Described nanometer Fe 3O 4Form be the rule spheroidal particle, median size is 50nm, and tool magnetic.The preparation method of nano-magnetic Z 250 is as follows: prepare certain density NaOH solution and place reaction vessel, heating in water bath, bath temperature are 70～90 ℃; Stirring and feed argon gas makes reaction vessel be in anaerobic state; Preparation finite concentration Fe 2(SO 4) 3And FeSO 47H 2The solution of O, and add a certain amount of vitriol oil to suppress Fe 2+Oxidation, wherein, Fe in the solution 3+With Fe 2+The ratio of amount of substance is 2: 1, and Fe 2+With OH in the NaOH solution -The scope of the ratio of amount of substance is 1: 10～1: 20, guarantees OH -Excessive; This mixing solutions is splashed in the reaction vessel with certain speed,, promptly generate nanometer Fe with the NaOH solution reaction 3O 4Particle; Reaction principle is Fe 2++ 2Fe 3++ 8OH -→ Fe 3O 4+ 4H 2O.Behind reaction 1～2h, with the synthetic nanometer Fe 3O 4Particle precipitation is used deionized water wash, and vacuum-drying promptly makes nanometer Fe 3O 4
Described reaction vessel can be the four-hole round-bottomed flask.
The principal reaction principle of handling waster water process is:
The dissolving and the H of iron have at first taken place simultaneously on the iron catalyst surface 2O 2Decomposition reaction, produced solvability iron (as Fe 2+And Fe 3+).With nanometer Fe 0During for catalyzer, formula 1 is seen in reaction; With nanometer Fe 3O 4During for catalyzer, formula 2 is seen in reaction; With nanometer Fe 0/ Fe 3O 4When mixture was catalyzer, formula 3 was seen in reaction.The Fe on iron catalyst surface 2+Will and H 2O 2Reaction produces hydroxyl radical free radical, simultaneously the Fe in the aqueous solution 2+Traditional Fenton reaction also can take place, and sees formula 4.Produce the relatively poor free radical HO of oxidisability subsequently 2And O 2 -, can make Fe 2+Regeneration (formula 5～8).Fe 3+With H 2O 2Reaction rate constant (formula 5) compare Fe 2+With H 2O 2Reaction rate constant (formula 4) little a lot, therefore play a major role in heterogeneous Fenton-like method degradation of organic substances process Chinese style 4.In the reaction process, exist some side reactions simultaneously, see formula 9～17.The OH that produces in the heterogeneous Fenton-like system is mainly by two kinds of approach and organic pollutant (RH) reaction: capture the hydrogen (seeing formula 18) on c h bond in the organism, N-H key or the O-H key; With two keys of C=C or aromatic ring reaction (seeing formula 19).When reacting with the chlorophenols organism, substitution reaction also may directly take place with the chlorine atom on the chlorophenol in hydroxyl radical free radical.Under aerobic conditions, RHOH can be further and O 2Formula 20 is seen in reaction.Intermediate product R, RHOH and ROH be further reaction under the effect of oxidizing substance, is degraded to CO at last 2, H 2O and small-molecule substance.
Fe 0 (s)+H 2O 2+2H +→Fe 2++2H 2O (1)
Fe 2+ magnetite+H 2O 2(aq)→Fe 3+ magnetite+·OH+OH - (2)
Fe 0/Fe 3O 4+H 2O 2→Fe 3+ surf+·OH+OH - (3)
Fe 2++H 2O 2→Fe 3++·OH+OH -，k＝63M -1s -1 (4)
Fe 3++H 2O 2→Fe 2++·HO 2+H +，k＝0.002-0.01M -1s -1 (5)
Figure BDA0000067970530000041
Fe 3++·HO 2→Fe 2++O 2+H +，k＝2.0×10 3M -1s -1 (7)
Fe 3++O 2· -→Fe 2++O 2，k＝5.0×10 7M -1s -1 (8)
H 2O 2+·OH→H 2O+·HO 2，k＝2.7×10 7M -1s -1 (9)
Fe 2++·OH→Fe 3++OH -，k＝3.2×10 8M -1s -1 (10)
Fe 2++·HO 2+H +→Fe 3++H 2O 2，k＝1.2×10 6M -1s -1 (11)
Fe 2++O 2· -+2H +→Fe 3++H 2O 2，k＝1.0×10 7M -1s -1 (12)
O 2· -+·HO 2+H +→H 2O 2+O 2，k＝9.7×10 7M -1s -1 (13)
·HO 2+·HO 2→H 2O 2+O 2，k＝8.3×10 5M -1s -1 (14)
·HO 2+·OH→H 2O+O 2，k＝7.1×10 9M -1s -1 (15)
O 2· -+·OH→OH -+O 2，k＝1.01×10 10M -1s -1 (16)
·OH+·OH→H 2O 2，k＝6.0×10 9M -1s -1 (17)
RH+·OH→R·+H 2O，k＝10 7-10 9M -1s -1 (18)
RH+·OH→RHOH· (19)
RHOH·+O 2→ROH+·HO 2，k＝10 8-10 9M -1s -1 (20)
Except OH, also may there be another kind of oxidizing substance Fe (IV) in the heterogeneous Fenton-like system, it can only come oxidation of organic compounds by transfer transport.In nanometer Fe 0, nanometer Fe 3O 4Or nanometer Fe 0/ Fe 3O 4The reaction that the mixture surface takes place is as follows:
Fe 2++H 2O 2→Fe(IV)+2OH - (20)
Fe(IV)+H 2O 2→Fe 2++O 2+2H + (21)
Fe(IV)+Fe 2+→2Fe 3+ (22)
Fe 3++·HO 2→Fe 2++O 2+H + (6)
Fe 3++O 2· -→Fe 2++O 2 (7)
·HO 2+·HO 2→H 2O 2+O 2 (13)
Beneficial effect of the present invention is mainly reflected in: treatment process is simple, and is easy to operate, and reagent is easy to get, the recyclable utilization of catalyzer, economically feasible; Can (pH 2.0～6.3) remove chlorinated organics efficiently, apace in wider pH range, thorough and non-secondary pollution has bigger application prospect.
Embodiment
The following examples can make those skilled in the art more fully understand the present invention, but do not limit the present invention in any way.
Embodiment 1
The preparation process of nano zero valence iron is as follows: add the FeSO that concentration is 4mM in the four-hole round-bottomed flask in advance 47H 2O solution 100mL stirs and feeds argon gas and makes it to be in anaerobic state, is the KBH of 20mM with concentration 4Solution 100mL splashes in the four-hole round-bottomed flask by variable valve, keeps stirring making solution be in the uniform mixing state, and behind the reaction 1.5h, with synthetic nano-iron particle precipitation, deionized water wash twice, vacuum-drying promptly makes nanometer Fe 0Nanometer Fe 0Form be the rule spheroidal particle, particle diameter is 80～150nm.
Experiment has been compared heterogeneous Fenton-like method and (has been added nanometer Fe simultaneously 0And H 2O 2), add nanometer Fe separately 0With independent adding H 2O 2Transformation efficiency, dechlorination rate and the TOC clearance of 4-chloro-3-methylphenol under three kinds of modes.
Nanometer Fe 0And H 2O 2In the heterogeneous Fenton-like reaction of coupling, the employing Erlenmeyer flask is a reactor, and treatment condition are for containing 4-chloro-3-methylphenol waste strength 100mg/L, and pH uncomfortable (pH 6.1) adds the 0.5g/L nanometer Fe simultaneously in reactor 0With 3mM H 2O 2Reactor is placed the water-bath oscillator, and rotating speed is 150rpm, and temperature is 30 ℃.
Add nanometer Fe separately 0In the experiment, add the 1.0g/L nano zero valence iron in reactor, other condition is the same.
Add H separately 2O 2In the experiment, in reactor, add 60mM H 2O 2, other condition is the same.
The wastewater treatment time is 15min, and result sees Table 1.
The comparison of three kinds of technologies of table 1
Figure BDA0000067970530000061
Detection method: 4-chloro-3-methylphenol adopts high performance liquid chromatograph, and (Agilent 1200 Series, Agilent USA) measure; Chlorion adopts ion chromatograph, and (DX-100, Dionex Germany) measure; The TOC value adopts total organic carbon/total blood urea/nitrogen analyzer, and (MultiN/C2100TOC/TN, Jena Germany) measure.
Table 1 is the result show, separately nanometer Fe 0With independent H 2O 2Technology all fails effectively to remove 4-chloro-3-methylphenol, and the treatment effect of heterogeneous Fenton-like method is fine.The present invention can be under the partial neutral condition (pH 6.1) handle fast and effectively and contain 4-chloro-3-methylphenol waste water, behind the reaction 15min, 4-chloro-3-methylphenol transformation efficiency is 99.6%, dechlorination rate is 80.5%, the TOC clearance is also higher.
Embodiment 2
The preparation process of magnetic Nano Z 250 is as follows: compound concentration is that the NaOH solution 100mL of 0.2M places the four-hole round-bottomed flask, 80 ℃ of waters bath with thermostatic control; Stirring and feed argon gas makes round-bottomed flask be in anaerobic state; Preparation Fe 2(SO 4) 3And FeSO 47H 2The solution 100mL of O, wherein, Fe 2(SO 4) 3And FeSO 47H 2The concentration of O is respectively 0.02M and 0.01M, adds a certain amount of vitriol oil to suppress Fe in solution 2+Oxidation; This mixing solutions is splashed in the four-hole round-bottomed flask with certain speed by variable valve,, promptly generate nanometer Fe with the NaOH solution reaction 3O 4Particle is behind the reaction 1.5h, with the synthetic nanometer Fe 3O 4Particle precipitation, deionized water wash twice, vacuum-drying promptly makes nanometer Fe 3O 4Nanometer Fe 3O 4Form be the rule spheroidal particle, median size is 50nm, and tool magnetic.
Experiment has been compared heterogeneous Fenton-like method and (has been added nanometer Fe simultaneously 3O 4And H 2O 2), add magnetic Nano Fe separately 3O 4With independent adding H 2O 2The difference of transformation efficiency, dechlorination rate and the TOC clearance of 4-chlorophenol under three kinds of modes.
Nanometer Fe 3O 4And H 2O 2In the heterogeneous Fenton-like reaction of coupling, 4-chlorophenol wastewater pH 2.0,4-chlorophenol waste water starting point concentration is 100mg/L, adds the 1.0g/L nanometer Fe simultaneously in reactor 3O 4And 30mMH 2O 2, reactor is placed the water-bath oscillator, rotating speed is 150rpm, temperature is 30 ℃.
Add nanometer Fe separately 3O 4In the experiment, 4-chlorophenol waste water ph is 5.8, adds the 1.0g/L nanometer Fe in reactor 3O 4, other condition is the same.
Add H separately 2O 2In the experiment, 4-chlorophenol waste water ph is 5.8, adds 30mMH in reactor 2O 2, other condition is the same.
The wastewater treatment time is 60min, and result sees Table 2.
Detection method: with embodiment 1.
The comparison of three kinds of technologies of table 2
Figure BDA0000067970530000081
Table 2 is the result show, separately nanometer Fe 3O 4With independent H 2O 2Technology all fails effectively to remove the 4-chlorophenol, and the treatment effect of heterogeneous Fenton-like method is better.The present invention can handle fast and effectively under acidic conditions and contain 4-chlorophenol waste water, and behind the reaction 60min, 4-chlorophenol transformation efficiency is 100%, and dechlorination rate is 89.9%, and the TOC clearance is 60.3%; Magnetic Nano Fe 3O 4Be easy to recycle.
Embodiment 3
The preparation process of nano zero valence iron is with embodiment 1; The preparation process of magnetic Nano Z 250 is with embodiment 2.
Adopt heterogeneous Fenton-like method to handle 4-chloro-3,5-xylenol waste water, waste water starting point concentration are 150mg/L, and pH uncomfortable (pH 6.3) adds the 1.0g/L nanometer Fe simultaneously 0/ Fe 3O 4Mixture (Fe wherein 0With Fe 3O 4Mass ratio is 1: 1) and 18mM H 2O 2, reactor is placed the water-bath oscillator, rotating speed is 150rpm, temperature is 30 ℃.Result sees Table 3.
Detection method: with embodiment 1.
Table 3 is the result show, heterogeneous Fenton-like method is handled 4-chloro-3, and the effect of 5-xylenol waste water is better, and behind the reaction 180min, 4-chloro-3, the transformation efficiency of 5-xylenol are up to 100%, and dechlorination rate and TOC clearance are also higher.
The heterogeneous Fenton-like method of table 3 is handled 4-chloro-3,5-xylenol waste water
Figure BDA0000067970530000091
Embodiment 4
The preparation process of nano zero valence iron is with embodiment 1; The preparation process of magnetic Nano Z 250 is with embodiment 2.
Adopt heterogeneous Fenton-like method to handle 4-chloro-3,5-xylenol waste water, waste water starting point concentration are 150mg/L, and pH uncomfortable (pH 6.3) adds the 1.0g/L nanometer Fe simultaneously 0/ Fe 3O 4Mixture and 18mM H 2O 2, change Fe 0And Fe 3O 4Mass ratio, reactor is placed the water-bath oscillator, rotating speed is 150rpm, temperature is 30 ℃.
The wastewater treatment time is 60min, and result sees Table 4.
Detection method: with embodiment 1.
Table 4 is the result show, at Fe 0With Fe 3O 4Quality is than (5: 1～1: 2) in the scope, the heterogeneous Fenton-like method 4-chloro-3 of can both degrading quickly and efficiently, 5-xylenol waste water.Of the present invention with nanometer Fe 0/ Fe 3O 4Mixture is that the heterogeneous Fenton-like method of catalyzer can rapidly and efficiently be handled chloride organic waste water under the partial neutral condition, and catalyzer is easy to recycle, and is having broad application prospects aspect the chlorinated organics processing of high density high toxicity difficult for biological degradation.
The heterogeneous Fenton-like method of table 4 is handled 4-chloro-3,5-xylenol waste water
Figure BDA0000067970530000101
The above; only for the preferable embodiment of the present invention, but protection scope of the present invention is not limited thereto, and anyly is familiar with those skilled in the art in the technical scope that the present invention discloses; the variation that can expect easily or replacement all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claim.

Claims (9)

1. the method for the chloride organic waste water of heterogeneous Fenton-like reaction treatment is characterized in that: with nanometer Fe 0, nanometer Fe 3O 4Or nanometer Fe 0/ Fe 3O 4Mixture is the Fenton-like catalyzer, at above-mentioned Fenton-like catalyzer and H 2O 2Exist simultaneously down and react with chloride organic waste water, with the degraded of the chlorinatedorganic in the waste water, wherein, nanometer Fe 0/ Fe 3O 4Mixture refers to the mixture of nano zero valence iron and magnetic Nano Z 250.
2. method according to claim 1 is characterized in that: nanometer Fe 0/ Fe 3O 4Fe in the mixture 0With Fe 3O 4Quality be (0.5～5) than scope: 1.
3. method according to claim 1 is characterized in that: the pH value of chloride organic waste water is 2.0～6.3.
4. method according to claim 1 is characterized in that: chloride organic waste water concentration is 80～160mg/L.
5. method according to claim 4 is characterized in that: nanometer Fe 0, nanometer Fe 3O 4Or nanometer Fe 0/ Fe 3O 4The consumption of mixture is 0.5～1.0g/L, H 2O 2Consumption is 3～30mM.
6. method according to claim 1 is characterized in that: nanometer Fe 0Form be the rule spheroidal particle, particle diameter is 80～150nm.
7. method according to claim 1 is characterized in that: nanometer Fe 3O 4Form be the rule spheroidal particle, median size is 50nm, and tool magnetic.
8. method according to claim 1 is characterized in that: nanometer Fe 0The preparation method be: in reaction vessel, add FeSO 47H 2O solution stirs and the feeding argon gas, with KBH 4Solution splashes in the reaction vessel, KBH 4Solution and FeSO 47H 2The volume ratio scope of O solution is 1: 1～2.5: 1, and the concentration ratio scope is 5: 1～8: 1, keeps stirring making solution be in the uniform mixing state, and behind reaction 1～2h, with synthetic nano-iron particle precipitation, deionized water wash promptly makes nanometer Fe after the vacuum-drying 0
9. method according to claim 1 is characterized in that: nanometer Fe 3O 4The preparation method be: NaOH solution is added in the reaction vessel, and heating in water bath, bath temperature are 70～90 ℃, stir also to feed argon gas; Preparation Fe 2(SO 4) 3And FeSO 47H 2The solution of O, and add the vitriol oil to suppress Fe 2+Oxidation, wherein, Fe in the solution 3+With Fe 2+The amount of substance ratio is 2: 1, and Fe 2+With OH in the NaOH solution -The scope of the ratio of amount of substance is 1: 10～1: 20; This mixing solutions is splashed in the reaction vessel,, promptly generate nanometer Fe with the NaOH solution reaction 3O 4Particle is behind reaction 1～2h, with the synthetic nanometer Fe 3O 4Particle precipitation, deionized water wash promptly makes nanometer Fe after the vacuum-drying 3O 4
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