CN1693225A - Multiphase catalysis oxydation sewage treatment method - Google Patents

Abstract

A process for treating the sewage containing phenol or the coking sewage by multi-phase catalytic oxidizing method features that the ratio of catalyst to sewage is 1-2 %, the ratio of hydrogen peroxide to sewage is 0.2-1.0% the treating temp is 55-70 deg.C and the catalyst contains Fe and one of Zn, Cu, Co and Mn.

Description

A kind of multiphase catalysis oxydation sewage treatment method

Technical field

The present invention relates to a kind of method of sewage disposal, be applicable to the method for coking chemical waste water and phenol-containing wastewater multiphase catalysis oxydation sewage treatment.

Background technology

Coking chemical waste water is the waste water that produces in coal system coke, gas purification and the coke chemicals removal process, is subjected to all multifactor influences such as raw coal character, coke making process, coke chemicals recovery, and its complicated component is changeable, belongs to unmanageable trade effluent.Hardly degraded organic substance matter occupies the majority in the coking chemical waste water, mainly contain phenols, polycyclic aromatic hydrocarbons, itrogenous organic substance and heterogeneous ring compound, wherein the phenolic compound based on phenol accounts for total amount of organic more than 70%, these components in the coking chemical waste water have a significant impact environment, phenolic compound particularly, can make protein coagulating, the mankind, aquatic products and farm crop are all had very big harm.

Processing for coking chemical waste water at present has following several method: (1) activated sludge process: this method adopts means acclimated microorganisms such as cultivation, modification, variation, reduce the restraining effect of organism to microorganism, reduce organism toxicity with reflux dilution or dosing coagulant, this method is difficult to reach emission standard.When the CODcr that enters the sudden and violent gas of active sludge pond waste water was the 2000mg/L left and right sides, water outlet CODcr was generally 350～700mg/L, and clearance is 65～85% only, and treatment effect is undesirable.(2) homogeneous catalysis oxidation style: H.J.H.Fenton (J.Chem.Soc.65 (1894) 899) discovery Fe in 1894 ²⁺Ion by hydrogen peroxide consumingly catalysis the oxidation of oxysuccinic acid, existing with oxygenant H ₂O ₂And catalyst Fe ²⁺Or Fe ³⁺Composition Fenton reagent.Fenton reagent oxidation method promptly belongs to homogeneous catalysis oxidation style, Fe ²⁺Or Fe ³⁺Can quicken H ₂O ₂Be decomposed into the OH free radical and make in the solution that organic pollutant is by the rapid oxidative degradation of OH free radical, this method speed of response is fast, processing efficiency is high, and clearance can be up to 90%.The shortcoming of this method is Fe in the solution ²⁺The concentration height, the water after the processing may have color, simultaneously the homogeneous catalysis Oxidation of Fe ²⁺Ion need constantly add, and the water after handling is wanted alkaline chemical precipitation Fe ²⁺Ion and regulator solution pH value make waste water treatment process complicated, and processing cost is also along with increase.(3) Catalytic Wet Oxidation; This method is a kind of treatment technology (US4699720 that handles the organic waste water of high density difficult for biological degradation that the eighties grows up in the world, 1987), it is to contain under the noble metal catalyst effect, directly the oxidation operation in the sewage is become CO with oxygen or air under high-temperature and high-pressure conditions ₂, H ₂Harmless objects such as O, to reach the purpose of purification, this method CODcr clearance can be up to 90～99%.But this method will be carried out under high temperature, the condition of high voltage in reactor.Because the cost height of this method catalyst system therefor, severe reaction conditions is difficult to promote the use of always.

Summary of the invention

The objective of the invention is to propose a kind of treatment process that is used for heterogeneous catalytic oxidation Treatment of Wastewater in Coking and phenol-containing wastewater.This method is easy and simple to handle, and temperature of reaction only needs 55～70 ℃, does not need to consume big energy, to organic pollutant removal rate height.

The method of a kind of multiphase catalysis oxydation sewage treatment that the present invention proposes, this method comprises following each step:

(1) weightmeasurement ratio of catalyzer and waste water is by 1～2g: 100ml takes by weighing catalyzer, adds in the waste water;

(2) use H ₂SO ₄Solution is regulated waste water to pH＜6;

(3) waste water that step (2) is obtained is heated to 55～70 ℃ and stirring, 30% H ₂O ₂Volume ratio 0.2～the 1ml of the consumption of solution and waste water: 100ml slowly is added drop-wise in the waste water solution, continues heated and stirred 10～20min;

(4) filtering separation.

The catalyzer that the present invention uses is number of patent application 200510011496.3, title: the catalyzer of " a kind of multiphase catalysis oxydation sewage treatment Catalysts and its preparation method " preparation.This catalyzer is the primary activity component with iron Fe, and a kind of among zinc Zn, copper Cu, cobalt Co or the manganese Mn is the auxiliary activity component.

The present invention compares the beneficial effect that is had with prior art:

The present invention is the phenol synthetic water of 5744mg/L through catalytic oxidation treatment CODcr value, handles back CODcr value and reduces to 64mg/L, and clearance is 98.8%; Handling the CODcr value is the phenol synthetic water of 2870mg/L, handles back CODcr value and reduces to＜20mg/L, and clearance is 99.3%; Handling the CODcr value is the phenol synthetic water of 1290mg/L, handles back CODcr value and reduces to＜20mg/L, and clearance is 98.4%; Treatment of Wastewater in Coking CODcr value can be reduced to below the 30mg/L by 1000mg/L, and well below discharging standards (less than 150mg/L), clearance is 97%.Adopt this method Treatment of Wastewater in Coking or phenol-containing wastewater, working method is easy, the processing efficiency height.

Description of drawings

The be untreated high pressure liquid chromatography figure of phenol simulated water sample (CODcr value for 2872mg/L) of Fig. 1.

Fig. 2 handles the high pressure liquid chromatography figure of back phenol simulated water sample.

Embodiment

Embodiment 1:

Get the phenol synthetic water of 100.0ml CODcr value, add the 2.0g catalyzer, use 10%H for 5744mg/L ₂SO ₄Stir in 68 ℃ of heating in water bath regulator solution pH＜6, slowly drips 2ml H ₂O ₂30% solution, reaction 20min after-filtration, the CODcr value of filtrate is reduced to 64mg/L, and clearance is 98.8%.

Embodiment 2:

Get the phenol synthetic water of 100.0ml CODcr value, add the 1.0g catalyzer, use 10%H for 2872mg/L ₂SO ₄Stir in 55 ℃ of heating in water bath regulator solution pH＜6, slowly drips 1ml H ₂O ₂30% solution, reaction 20min after-filtration, the CODcr value of filtrate is reduced to＜20mg/L, and clearance is 99.3%.High pressure liquid chromatography figure before and after handling sees accompanying drawing.

Embodiment 3:

Get the coking chemical waste water of 50.0ml CODcr value, add the 1.0g catalyzer, use 10%H for 505mg/L ₂SO ₄Stir in 60 ℃ of heating in water bath regulator solution pH＜6, slowly drips 1ml H ₂O ₂30% solution, reaction 20min after-filtration, the CODcr value of filtrate is reduced to＜20mg/L, clearance＞96%.

Fig. 1 is the peak area that there is very big phenol at the 3.137min place in retention time for the high pressure liquid chromatography figure of the phenol simulated water sample that is untreated (the CODcr value is 2872mg/L) as can be seen from Figure 1.

Fig. 2 handles the high pressure liquid chromatography figure of back phenol simulated water sample, and the peak area of phenol is very little has as can be seen from Figure 2 disappeared basically, illustrates by catalyzed oxidation and constitutionally stable phenyl ring has been opened.

Claims (1)

1. a heterogeneous catalytic oxidation is handled the treatment process of phenol-containing wastewater and coking chemical waste water, it is characterized in that: the concrete steps of this treatment process:

(1) weightmeasurement ratio of catalyzer and waste water is by 1～2g: 100ml takes by weighing catalyzer, adds in the waste water;

(2) use H ₂SO ₄Solution is regulated waste water to pH＜6;

(3) waste water that step (2) is obtained is heated to 55～70 ℃ and stirring, 30% H ₂O ₂Volume ratio 0.2～the 1ml of the consumption of solution and waste water: 100ml slowly is added drop-wise in the waste water solution, continues heated and stirred 10～20min;

(4) filtering separation.

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