CN102295341B - 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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CN102295341B
CN102295341B CN201110158185.5A CN201110158185A CN102295341B CN 102295341 B CN102295341 B CN 102295341B CN 201110158185 A CN201110158185 A CN 201110158185A CN 102295341 B CN102295341 B CN 102295341B
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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

A kind of heterogeneous Fenton-like reaction is processed the method for chlorine organic wastewater
Technical field
The invention belongs to environmental protection technical field, be specifically related to a kind of method that heterogeneous Fenton-like reaction is processed chlorine organic wastewater.
Background technology
Chlorinatedorganic comprises hydrochloric ether, chlorination aromatic hydrocarbon, organochlorine insecticide etc., is widely used in the industries such as printing and dyeing, papermaking, dry-cleaning, metal parts processing, electronic equipment manufacturing, organic pesticide.Because of its numerous sources, their existence can be detected now in surface water, underground water and soil.Chlorine organic wastewater toxicity is large, and difficult for biological degradation has " three cause effect ", and ecotope and human health have been caused to direct destruction and potential threat.Therefore, research treatment technology economic, efficient, non-secondary pollution has great importance.
Traditional water treatment method, as absorption, flocculation, precipitation, biological process etc. have, efficiency is low, cost is high, easily produce the limitation such as secondary pollution.In recent years, the high-level oxidation technology in chemical method becomes the focus that people pay close attention to gradually, and it utilizes the hydroxyl radical free radical that oxidisability is very strong (OH) to carry out the organic pollutant in oxygenolysis water.Wherein, Fenton reagent (being the combination of ferrous salt and hydrogen peroxide) is on the increase for the research of removing organic pollutants.The action principle of the 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 ferrous ion.With other advanced oxidation processes, compare, Fenton reagent method has rapidly and efficiently, operating process is simple, without complex apparatus, to follow-up processing toxicological harmless effect and the 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, before reaction and after reaction, needs to regulate the pH value; After having reacted, need the iron ion in solution be separated by methods such as precipitations, the expense of aftertreatment is more high.
For overcoming many deficiencies of homogeneous phase Fenton reaction, a lot of scholars are studied heterogeneous Fenton-like system.So-called heterogeneous Fenton-like oxidation system is that the heterogeneous iron of use is ferrous salt and hydrogen peroxide or the oxygen reaction that solid catalyst replaces homogeneous phase; In these systems, thereby can discharging from surface ferrous ion, the solid iron catalyzer come catalyzing hydrogen peroxide to excite the Fenton reaction as homogeneous catalyst.Heterogeneous Fenton-like reaction can carry out in wider pH scope, have that rate of oxidation is high, the catalyzer source is wide, be easy to recycle and reaction process in can not produce the advantage such as a large amount of ferriferous oxide precipitations, provide wide prospect for processing 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 wider pH scope (pH 2.0～6.3) remove waste water efficiently in the heterogeneous Fenton-like oxidation style of chlorinated organics.
A kind of heterogeneous Fenton-like reaction is processed the method for chlorine organic wastewater, and the 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 2under existing, with chlorine organic wastewater, react simultaneously, by the degraded of the chlorinatedorganic in 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 mixture 0with Fe 3o 4the optimization quality than scope, be (0.5～5): 1.
The pH value of described chlorine organic wastewater is 2.0～6.3.
When chlorine organic wastewater 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 regular spheroidal particle, particle diameter is 80～150nm.Nanometer Fe 0the preparation method be: add in advance certain density FeSO in reaction vessel 47H 2o solution, stir and pass into argon gas and make it in anaerobic state, by certain density KBH 4solution splashes in 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 reaction process and keep reaction to carry out under anaerobic state, micro-bubble the adhering to core and preventing nanometer Fe as iron atom that aeration produces 0the reunion of particle, keep stirring to make solution in even admixture.After reaction 1～2h, by synthetic nano-iron particle precipitation, with making nanometer Fe after deionized water wash vacuum-drying 0.
Described nanometer Fe 3o 4form be regular spheroidal particle, median size is 50nm, and tool magnetic.The preparation method of Nanometer Magnetite is as follows: prepares certain density NaOH solution and is placed in reaction vessel, and heating in water bath, bath temperature is 70～90 ℃; Stirring and pass into argon gas makes reaction vessel 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 solution 3+with Fe 2+the ratio of amount of substance is 2: 1, and Fe 2+with OH in 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 reaction vessel with certain speed, with the NaOH solution reaction, generate nanometer Fe 3o 4particle; Reaction principle is Fe 2++ 2Fe 3++ 8OH -→ Fe 3o 4+ 4H 2o.After reaction 1～2h, by synthetic nanometer Fe 3o 4particle precipitation, use deionized water wash, and vacuum-drying make nanometer Fe 3o 4.
Described reaction vessel can be the four-hole round-bottomed flask.
The principal reaction principle of processing waster water process is:
At first dissolving and the H of iron have occurred on the iron catalyst surface simultaneously 2o 2decomposition reaction, produced solvability iron (as Fe 2+and Fe 3+).With nanometer Fe 0during for catalyzer, formula 1 is shown in reaction; With nanometer Fe 3o 4during for catalyzer, formula 2 is shown in reaction; With nanometer Fe 0/ Fe 3o 4when mixture is catalyzer, formula 3 is shown 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 occur, and sees formula 4.Produce subsequently the poor free radical HO of oxidisability 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 in heterogeneous Fenton-like method degradation of organic substances process Chinese style 4, play a major role.In reaction process, exist some side reactions simultaneously, see formula 9～17.The OH produced in heterogeneous Fenton-like system mainly reacts with organic pollutant (RH) by two kinds of approach: capture the hydrogen (seeing formula 18) on c h bond in organism, N-H key or O-H key; React (seeing formula 19) with the two keys of C=C or aromatic ring.While reacting with the chlorophenols organism, hydroxyl radical free radical also may with chlorophenol on the chlorine atom substitution reaction directly occurs.Under aerobic conditions, RHOH can be further and O 2reaction, be shown in formula 20.Intermediate product R, RHOH and ROH be further reaction under the effect of oxidizing substance, finally is degraded to CO 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 is another kind of oxidizing substance Fe (IV) in heterogeneous Fenton-like system, it can only carry out 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 occurs 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, easy to operate, and reagent is easy to get, catalyzer recoverable, economically feasible; Can in wider pH range, (pH 2.0～6.3) remove efficiently, rapidly chlorinated organics, thorough and non-secondary pollution, have larger 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 in advance the FeSO that concentration is 4mM in the four-hole round-bottomed flask 47H 2o solution 100mL, stir and pass into argon gas and make it in anaerobic state, the KBH that is 20mM by concentration 4solution 100mL splashes in the four-hole round-bottomed flask by variable valve, keeps stirring making solution in even admixture, and after reaction 1.5h, by synthetic nano-iron particle precipitation, deionized water wash twice, vacuum-drying make nanometer Fe 0.Nanometer Fe 0form be regular 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 0add separately H 2o 2transformation efficiency, dechlorination rate and the TOC clearance of the chloro-3-methylphenol of 4-under three kinds of modes.
Nanometer Fe 0and H 2o 2in the heterogeneous Fenton-like reaction of coupling, the employing Erlenmeyer flask is reactor, and treatment condition are for containing the chloro-3-methylphenol of 4-waste strength 100mg/L, and pH uncomfortable (pH 6.1) adds the 0.5g/L nanometer Fe in reactor simultaneously 0with 3mM H 2o 2reactor is placed in to the water-bath oscillator, and rotating speed is 150rpm, and temperature is 30 ℃.
Add separately nanometer Fe 0in experiment, in reactor, add the 1.0g/L nano zero valence iron, other condition is the same.
Add separately H 2o 2in experiment, in reactor, add 60mM H 2o 2, other condition is the same.
The wastewater treatment time is 15min, and result is in Table 1.
The comparison of three kinds of techniques of table 1
Figure BDA0000067970530000061
The chloro-3-methylphenol of detection method: 4-adopts high performance liquid chromatograph (Agilent 1200 Series, Agilent, USA) to measure; Chlorion adopts ion chromatograph (DX-100, Dionex, Germany) to measure; The TOC value adopts total organic carbon/total blood urea/nitrogen analyzer (MultiN/C2100TOC/TN, Jena, Germany) to measure.
Table 1 result shows, independent nanometer Fe 0with independent H 2o 2technique all fails effectively to remove the chloro-3-methylphenol of 4-, and the treatment effect of heterogeneous Fenton-like method is fine.The present invention can (pH 6.1) process fast and effectively containing the chloro-3-methylphenol of 4-waste water under the partial neutral condition, and after reaction 15min, the chloro-3-methylphenol of 4-transformation efficiency is 99.6%, and dechlorination rate is that 80.5%, TOC clearance is also higher.
Embodiment 2
The preparation process of magnetic Nano Z 250 is as follows: the NaOH solution 100mL that compound concentration is 0.2M is placed in the four-hole round-bottomed flask, 80 ℃ of waters bath with thermostatic control; Stirring and pass into argon gas makes round-bottomed flask 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, in solution, adds a certain amount of vitriol oil to suppress Fe 2+oxidation; This mixing solutions is splashed in the four-hole round-bottomed flask with certain speed by variable valve, with the NaOH solution reaction, generate nanometer Fe 3o 4particle, after reaction 1.5h, by synthetic nanometer Fe 3o 4particle precipitation, deionized water wash twice, vacuum-drying make nanometer Fe 3o 4.Nanometer Fe 3o 4form be regular 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 4add separately 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 pH 2.0,4-Chlorophenol starting point concentration is 100mg/L, adds the 1.0g/L nanometer Fe in reactor simultaneously 3o 4and 30mMH 2o 2, reactor is placed in to the water-bath oscillator, rotating speed is 150rpm, temperature is 30 ℃.
Add separately nanometer Fe 3o 4in experiment, 4-Chlorophenol pH value is 5.8, in reactor, adds the 1.0g/L nanometer Fe 3o 4, other condition is the same.
Add separately H 2o 2in experiment, 4-Chlorophenol pH value is 5.8, in reactor, adds 30mMH 2o 2, other condition is the same.
The wastewater treatment time is 60min, and result is in Table 2.
Detection method: with embodiment 1.
The comparison of three kinds of techniques of table 2
Figure BDA0000067970530000081
Table 2 result shows, independent nanometer Fe 3o 4with independent H 2o 2technique all fails effectively to remove the 4-chlorophenol, and the treatment effect of heterogeneous Fenton-like method is better.The present invention can process fast and effectively containing the 4-Chlorophenol under acidic conditions, and after reaction 60min, 4-chlorophenol transformation efficiency is 100%, and dechlorination rate is that 89.9%, 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 process CDMP waste water, the waste water starting point concentration is 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 in to the water-bath oscillator, rotating speed is 150rpm, temperature is 30 ℃.Result is in Table 3.
Detection method: with embodiment 1.
Table 3 result shows, heterogeneous Fenton-like method processes that the effect of CDMP waste water is better, and after reaction 180min, the transformation efficiency of CDMP is up to 100%, and dechlorination rate and TOC clearance are also higher.
The heterogeneous Fenton-like method of table 3 is processed CDMP 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 process CDMP waste water, the waste water starting point concentration is 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 in to the water-bath oscillator, rotating speed is 150rpm, temperature is 30 ℃.
The wastewater treatment time is 60min, and result is in Table 4.
Detection method: with embodiment 1.
Table 4 result shows, at Fe 0with Fe 3o 4quality is than (5: 1～1: 2) in scope, the heterogeneous Fenton-like method CDMP waste water of can degrading quickly and efficiently.Of the present invention with nanometer Fe 0/ Fe 3o 4the heterogeneous Fenton-like method that mixture is catalyzer can rapidly and efficiently be processed chlorine organic wastewater under the partial neutral condition, and catalyzer is easy to recycle, and aspect the chlorinated organics processing of high density high toxicity difficult for biological degradation, is having broad application prospects.
The heterogeneous Fenton-like method of table 4 is processed CDMP waste water
Figure BDA0000067970530000101
The above; be only the present invention's embodiment preferably, but protection scope of the present invention is not limited to this, anyly is familiar with in technical scope that those skilled in the art disclose in the present invention; the variation that can expect easily or replacement, within all should being encompassed in 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 (6)

1. the method for a heterogeneous Fenton-like reaction processing chlorine organic wastewater, is characterized in that: with nanometer Fe 0/ Fe 3o 4mixture is the Fenton-like catalyzer, at above-mentioned Fenton-like catalyzer and H 2o 2under existing, with chlorine organic wastewater, react simultaneously, by the degraded of the chlorinatedorganic in waste water, wherein, nanometer Fe 0/ Fe 3o 4mixture refers to the mixture of nano zero valence iron and magnetic Nano Z 250; Wherein the pH value of chlorine organic wastewater is 6.3;
Described nanometer Fe 0the preparation method be: add FeSO in reaction vessel 47H 2o solution, stir and pass into argon gas, by KBH 4solution splashes in 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 in even admixture, and after reacting 1～2h, by synthetic nano-iron particle precipitation, deionized water wash, make nanometer Fe after vacuum-drying 0;
Described nanometer Fe 3o 4the preparation method be: NaOH solution is added in reaction vessel, heating in water bath, bath temperature is 70～90 ℃, stirs and pass into 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 solution 3+with Fe 2+amount of substance is than being 2:1, and Fe 2+with OH in NaOH solution -the scope of the ratio of amount of substance is 1:10～1:20; This mixing solutions is splashed in reaction vessel, with the NaOH solution reaction, generate nanometer Fe 3o 4particle, after reacting 1～2h, by synthetic nanometer Fe 3o 4particle precipitation, deionized water wash, make nanometer Fe after vacuum-drying 3o 4.
2. method according to claim 1, is characterized in that: nanometer Fe 0/ Fe 3o 4fe in mixture 0with Fe 3o 4quality than scope, be (0.5～5): 1.
3. method according to claim 1, it is characterized in that: chlorine organic wastewater concentration is 80～160mg/L.
4. method according to claim 1, is characterized in that: nanometer Fe 0/ Fe 3o 4the consumption of mixture is 0.5～1.0g/L, H 2o 2consumption is 3～30mM.
5. method according to claim 1, is characterized in that: nanometer Fe 0form be regular spheroidal particle, particle diameter is 80～150nm.
6. method according to claim 1, is characterized in that: nanometer Fe 3o 4form be regular spheroidal particle, median size is 50nm, and tool magnetic.
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"纳米零价铁的制备及其去除水中对氯硝基苯的研究";董婷婷等;《环境工程学报》;20100630;第4卷(第6期);"纳米零价铁的制备及其去除水中对氯硝基苯的研究" *
周涛."氯酚类物质在零价铁强化还原/氧化体系中的降解研究".《中国优秀硕士学位论文全文数据库 工程科技I辑》.2009,(第5期),第51-55页.
董婷婷等."纳米零价铁的制备及其去除水中对氯硝基苯的研究".《环境工程学报》.2010,第4卷(第6期),"纳米零价铁的制备及其去除水中对氯硝基苯的研究".

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