CN102229442B - Method for treating printing and dyeing wastewater with rare earth cerium doped titanium-based manganese dioxide electrode - Google Patents

Method for treating printing and dyeing wastewater with rare earth cerium doped titanium-based manganese dioxide electrode Download PDF

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CN102229442B
CN102229442B CN 201110098814 CN201110098814A CN102229442B CN 102229442 B CN102229442 B CN 102229442B CN 201110098814 CN201110098814 CN 201110098814 CN 201110098814 A CN201110098814 A CN 201110098814A CN 102229442 B CN102229442 B CN 102229442B
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electrode
cerium doped
manganese dioxide
titanium
rare
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CN102229442A (en
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周笑绿
谭小文
张艳艳
李环
商菲
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Shanghai University of Electric Power
University of Shanghai for Science and Technology
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Shanghai University of Electric Power
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Abstract

The invention discloses a method for treating printing and dyeing wastewater with a rare earth cerium doped titanium-based manganese dioxide electrode. The electrode comprises a titanium base, an interlayer of tin/antimony oxide and a surface coating of rare earth cerium doped manganese dioxide. According to the treating method provided in the invention, the rare earth cerium doped titanium-based manganese dioxide electrode is used as the anode, and a titanium plate is used as the cathode; distance between plate electrodes is 2.5 to 7 cm; the electrolyte sodium chloride has a concentration of 0.1 mol/L and a pH value of 8 to 10; current density is 30 mA/cm<2>; electrolysis lasts for 1 to 1.5 h. When simulated printing and dyeing wastewater is treated with the prepared rare earth cerium doped titanium-based manganese dioxide electrode, removal rate of chroma in the wastewater is more than 96% and removal rate of COD reaches 84% to 91%.

Description

The method of utilizing rare-earth cerium doped Ti supported manganese dioxide electrode pair dyeing waste water to process
Technical field
The invention belongs to Material Field and technical field of waste water processing, be specifically related to a kind of rare-earth cerium doped Ti supported manganese dioxide electro catalytic electrode that utilizes The method that dyeing waste water is processed
Background technology
Printing and dyeing industry is the discharge of wastewater rich and influential family, and a year wastewater discharge accounts for more than 1/10 of trade effluent total amount, is one of current water body primary pollution source.The all the time processing of dyeing waste water all belongs to the difficult point in the trade effluent, and it has, and colourity is large, organic pollutant content high, change of water quality is large, complicated component and contain the characteristics of bio-refractory material.
In recent years because dyeing exploitation and used many new raw materials, reactive monoazo dyestuffs, new auxiliary, so that the intractability of dyeing waste water strengthens, original biological treatment system COD clearance drops to about 50% from 70%, even lower; Traditional Coagulation Method and oxidation style also only are about 30% to the COD clearance of this class dyeing waste water.The biological treatment long processing period, Coagulation Method and chemical oxidization method may produce secondary pollution, and the present invention proposes for the problems referred to above just, adopt treatment process of the present invention after, final chroma in waste water clearance reaches more than 96%, and the COD clearance reaches 84%～91%.The novel electrode of developing and treatment process are expected that treatment of dyeing wastewater is had positive pushing effect.
Summary of the invention
The present invention is in order to solve the problems such as existing long processing period in the above-mentioned treatment of dyeing wastewater, processing efficiency be low and a kind of utilization is provided Rare-earth cerium doped Ti supported manganese dioxide electrodeTo the method that dyeing waste water is processed, it has, and treatment cycle is short, the processing efficiency high.
Technical scheme of the present invention
A kind of method of utilizing cerium doped titanium-base manganese dioxide electrode that dyeing waste water is processed, its treatment step is as follows:
Be that the electrolyzer anode is rare-earth cerium doped Ti supported manganese dioxide electrode, negative electrode is titanium plate or stainless steel electrode, and ionogen is sodium-chlor, and concentration 0.1 mol/L, pH are 8～10; The battery lead plate spacing adopts 2.5～7cm, and current density is 30mA/cm 2, electrolysis 1～1.5h.
Rare-earth cerium doped its structure iron of Ti supported manganese dioxide electrode described above as shown in Figure 1, it is made of internal layer titanium matrix 1, tin-antimony oxide middle layer 2 and rare-earth cerium doped Manganse Dioxide top coat 3;
Described internal layer titanium matrix is pure titanium plate, thickness 3mm;
Described tin-antimony oxide middle layer is SnO 2And Sb 2O 5The mixture that forms, the mol ratio of tin and antimony is 3.7:1 in the mixture, thickness is about 30 μ m;
The mol ratio of described rare-earth cerium doped Manganse Dioxide top coat middle-weight rare earths cerium and Manganse Dioxide is 1:25～50, and thickness is about 100 μ m.
The preparation method of described cerium doped titanium-base manganese dioxide electrode is: titanium base stage plate pass through successively polishing, alkali cleaning, pickling, harsh after, the middle layer of repetitive coatings preparation and the masking liquid of upper layer, and carry out respectively thermal decomposition process.The electrode composition is expressed as Ti/SnO 2-SbO X/ MnO 2(Ce).
Described cerium doped titanium-base manganese dioxide electrode, its concrete preparation process is as follows:
(1), the pre-treatment of titanium matrix:
Pure titanium plate is as matrix, use 200#, 600#, 1200#, the abrasive paper for metallograph of 1500# to the surface of titanium matrix polish successively to smooth smooth after, use saturated sodium hydroxide solution to boil 30min and carry out oil removal treatment, soak 2h with 1:1 nitric acid+sulfuric acid again, then in 10% oxalic acid solution, corrode about 25min, treat that the sorrel material occurs, form pitted skin titanium matrix, use at last washed with de-ionized water, be immersed in the dehydrated alcohol for subsequent use;
(2), the preparation in tin-antimony oxide middle layer:
Take by weighing SnCl 45H 2O 0.85g, SbCl 30.15g, measure concentrated hydrochloric acid 1ml, propyl carbinol 4ml is mixed with the middle layer masking liquid, with hairbrush with the even scrubbing brush of this masking liquid on the surface of step (1) through the pitted skin titanium matrix of pre-treatment, oven dry is rear at 500 ℃ of lower sintering 10min, this process repetitive coatings 6 times, at last at 550 ℃ of lower sintering 30min, the final electrode that gets tin-antimony oxide compound middle layer;
(3), the preparation of rare-earth cerium doped Manganse Dioxide top coat top coat
Utilize 50% manganese nitrate solution and a certain amount of cerous nitrate preparation top coat masking liquid, with hairbrush masking liquid is coated in the electrode surface that step (2) has prepared tin-antimony oxide compound middle layer equably, at 90 ℃ of lower dry 10min, afterwards at 200 ℃ of lower thermolysis 5min, this process repetitive coatings 30 times, last sintering 20min under 350 ℃ obtains rare-earth cerium doped Ti supported manganese dioxide electrode.
Beneficial effect of the present invention
The method that the present invention utilizes cerium doped titanium-base manganese dioxide electrode that the simulation dyeing waste water is processed, compare with traditional methods such as biological treatment, coagulation and chemical oxidation, the method has characteristics such as removing that efficient is high, speed is fast, take up an area less, reaction controllable degree height and secondary pollution are few.The present invention utilizes cerium doped titanium-base manganese dioxide electrode that the simulation dyeing waste water is processed, and along with the increase of electrolysis time, the COD clearance raises gradually.When with the cerium doped titanium-base manganese dioxide electrode of preparation the dyeing waste water of simulation being processed, final chroma in waste water clearance reaches more than 96%, and the COD clearance preferably reaches 84%～91%.Therefore the method for utilizing cerium doped titanium-base manganese dioxide electrode that dyeing waste water is processed of the present invention is a kind of quick, effective, easy treatment method of printing and dying wastewater of popularizing of working method.
Description of drawings
The structural representation of Fig. 1, rare-earth cerium doped Ti supported manganese dioxide electrode
The impact that Fig. 2, electrolysis time are removed simulating color degree of dyeing waste water and COD
Fig. 3,2 kinds of electrode pair simulation disposal effect of dyeing wastewaters, the TSM-5 electrode is the Ti supported manganese dioxide electrode of 5% cerium concentration that mixes among the figure, the TSM-10 electrode is the Ti supported manganese dioxide electrode of 10% cerium concentration that mixes.
Embodiment
Also by reference to the accompanying drawings the present invention is further set forth below by embodiment, but do not limit the present invention.
The various instruments that the present invention is used:
The program control cabinet-type electric furnace of SXL-1208 type (the upper grand testing installation of Nereid company limited);
Electric heating constant-temperature blowing drying box DHG-9076A type (the accurate experimental installation in Shanghai company limited);
SW171501SL-2A type voltage stabilized source (regulator factory, Shanghai);
WFJ-7200 type ultraviolet-visible photometer (Shanghai You Nike Instr Ltd.);
The accurate pH meter (Shanghai Precision Scientific Apparatus Co., Ltd) of PHS-3C.
The all ingredients that the present invention is used:
50% manganese nitrate solution (Shanghai permanent letter chemical reagent company limited);
Crystallization tin tetrachloride (Chemical Reagent Co., Ltd., Sinopharm Group);
Butter of antimony (Shishewei Chemical Co., Ltd., Shanghai);
Cerous nitrate (those chemical reagent company limiteds of Shanghai dust);
Methylene blue (upper seamount Pu chemical industry company limited);
Above reagent is the analytical pure rank.
Embodiment 1
The mix preparation of Ti supported manganese dioxide electrode (being abbreviated as the TSM-5 electrode) of 5% cerium concentration comprises the steps:
(1), the pre-treatment of titanium matrix
Namely use 200#, 600#, 1200#, the abrasive paper for metallograph of 1500# to the surface of titanium matrix polish successively to smooth smooth after, use saturated sodium hydroxide solution to boil 30min and carry out oil removal treatment, soak 2h with 1:1 nitric acid+sulfuric acid again, then harsh about 25min in 10% oxalic acid solution treats that the sorrel material occurs, and forms pitted skin titanium matrix, use at last washed with de-ionized water, be immersed in the dehydrated alcohol;
(2), the preparation in tin-antimony oxide middle layer
Get SnCl 45H 2O0.85g, SbCl 30.15g, HCl (36%) 1mL, propyl carbinol 4ml is mixed with the middle layer masking liquid, with hairbrush with the even scrubbing brush of this masking liquid on the titanium matrix surface, the oven dry after in 500 ℃ of lower sintering 10min, repetitive coatings 6 times, at 550 ℃ of lower sintering 30min, just generate the SnO of even thickness at last 2+ Sb 2O 5Middle layer, thickness are about 30 μ m;
(3), the preparation of rare earth doped Manganse Dioxide top coat
Use 50wt%Mn(NO 3) 2Solution is that the 50:1 ratio adds cerous nitrate in manganese and cerium mol ratio, is mixed with 1moldm with distilled water diluting -3The upper layer masking liquid, masking liquid is coated in equably on the electrode surface that has prepared the middle layer with hairbrush, at 90 ℃ of lower dry 10min, then at 200 ℃ of lower thermolysis 5min, this process repetitive coatings 30 times at 350 ℃ of lower sintering 20min, finally obtains TSM-5 electrode of the present invention at last, its top coat thickness is about 100 μ m, and the electrode of gained is grey black.
Embodiment 2
The mix preparation of Ti supported manganese dioxide electrode (being abbreviated as the TSM-10 electrode) of 10% cerium concentration comprises the steps:
(1), the pre-treatment of titanium matrix (with embodiment 1);
(2), the preparation in tin-antimony oxide middle layer (with embodiment 1);
(3), the preparation of rare earth doped Manganse Dioxide top coat
Use 50wt%Mn(NO 3) 2Solution is that the 25:1 ratio adds cerous nitrate in manganese and cerium mol ratio, is mixed with 1moldm with distilled water diluting -3The upper layer masking liquid, masking liquid is coated in equably on the electrode surface that has prepared the middle layer with hairbrush, at 90 ℃ of lower dry 10min, then at 200 ℃ of lower thermolysis 5min, this process repetitive coatings 30 times, at 350 ℃ of lower sintering 20min, finally obtain TSM-10 electrode of the present invention at last, its top coat thickness is about 100 μ m.
Application Example 1
Utilize the TSM-5 electrode treatment of simulated dyeing waste water test of embodiment 1 preparation.
Adopting the TSM-5 electrode is anode, and the titanium plate is negative electrode, and interelectrode distance is 7cm, and to the sodium chloride electrolysis matter of 600ml simulation methylene blue waste water at normal temperature, 0.1mol/L, electrolysis density is 30mA/cm 2, pH is 9, carries out electrolysis treatment under the electrolysis time 1.5h condition, chroma removal rate is that 96.9%, COD clearance is 91.8% after the wastewater treatment.Simulation dyeing waste water water quality: COD is 317.6mg/L, and colourity spectrophotometry, waste water record its absorbance under 660nm be 2.623.
Accompanying drawing 2 is for utilizing the degradation effect figure of TSM-5 electrode treatment of simulated dyeing waste water.As can be seen from Figure 2 along with the increase of electrolysis time, the COD clearance raises gradually, and when electrolysis time was 60min, COD and chroma removal rate were all more than 80 percent, and when electrolysis time was 80min, the COD clearance reached more than 90 percent; Chroma removal rate is then close to a hundred per cent.
Application Example 2
Utilize TSM-5 electrode, embodiment 2 gained TSM-10 electrodes and the titanium plate electrode of embodiment 1 gained to come the simultaneous test of respectively the simulation dyeing waste water being processed.
Utilize respectively above-mentioned 3 kinds of electrodes to be anode, the titanium plate is negative electrode, and interelectrode distance is 2.5cm, and to the sodium chloride electrolysis matter of 200ml simulation methylene blue waste water at normal temperature, 0.1mol/L, electrolysis density is 30mA/cm 2, pH is 9, carries out electrolysis treatment under the electrolysis time 1.5h condition, simulation dyeing waste water water quality: COD is 535.5mg/L, behind the colourity spectrophotometry, 5 times of wastewater dilutions under the 660nm absorbance be 2.601.Experimental result is seen accompanying drawing 3.The Ti supported manganese dioxide electrode general effect of two kinds of cerium doping contents is far above the effect of titanium plate electrode as can be seen from Figure 3, the TSM-5 electrode is processed the chroma removal rate of waste water greater than 96.9%, the COD clearance is greater than 66%, the TSM-10 electrode is processed the chroma removal rate of waste water greater than 96%, the COD clearance reaches 84%～91%, and the chroma removal rate of titanium plate electrode only is 11%, and the COD clearance only is 27%.
Above said content only is the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.

Claims (2)

1. method of utilizing cerium doped titanium-base manganese dioxide electrode that dyeing waste water is processed, it is characterized in that treatment step is: the electrolyzer anode is rare-earth cerium doped Ti supported manganese dioxide electrode, negative electrode is titanium plate or stainless steel plate electrode, the battery lead plate spacing is 2.5～7cm, employing sodium-chlor is ionogen, concentration is 0.1 mol/L, and pH is 8～10, and the control current density is 30mA/cm 2, normal temperature, electrolysis 1～1.5h under the magnetic agitation; Used rare-earth cerium doped Ti supported manganese dioxide electrode is made of the internal layer titanium matrix of thickness 3mm, the tin-antimony oxide middle layer of thickness 30 μ m and the rare-earth cerium doped Manganse Dioxide top coat that thickness is 100 μ m; Described internal layer titanium matrix is pure titanium plate; Described tin-antimony oxide middle layer is SnO 2And Sb 2O 5The mixture that forms, the mol ratio of tin and antimony is 3.7:1 in the mixture; The mol ratio of described rare-earth cerium doped Manganse Dioxide top coat middle-weight rare earths cerium and Manganse Dioxide is 1:25～50.
2. cerium doped titanium-base manganese dioxide electrode as described in claim 1 is characterized in that the preparation method of described rare-earth cerium doped Ti supported manganese dioxide electrode comprises the steps;
(1), the pre-treatment of titanium matrix:
Pure titanium plate is as matrix, use 200#, 600#, 1200#, the abrasive paper for metallograph of 1500# to the surface of titanium matrix polish successively to smooth smooth after, use saturated sodium hydroxide solution to boil 30min and carry out oil removal treatment, soak 2h with 1:1 nitric acid+sulfuric acid again, then in 10% oxalic acid solution, corrode 25min, treat that the sorrel material occurs, form pitted skin titanium matrix, use at last washed with de-ionized water, be immersed in the dehydrated alcohol for subsequent use;
(2), the preparation in tin-antimony oxide middle layer:
Take by weighing SnCl 45H 2O 0.85g, SbCl 30.15g, measure concentrated hydrochloric acid 1ml, propyl carbinol 4ml is mixed with the middle layer masking liquid, with hairbrush with the even scrubbing brush of this masking liquid on the surface of step (1) through the pitted skin titanium matrix of pre-treatment, oven dry is rear at 500 ℃ of lower sintering 10min, this process repetitive coatings 6 times at last at 550 ℃ of lower sintering 30min, finally obtains the electrode in tin-antimony oxide compound middle layer;
(3), the preparation of rare-earth cerium doped Manganse Dioxide top coat top coat
Utilize 50% manganese nitrate solution and a certain amount of cerous nitrate preparation top coat masking liquid, with hairbrush masking liquid is coated in the electrode surface that step (2) has prepared tin-antimony oxide compound middle layer equably, at 90 ℃ of lower dry 10min, afterwards at 200 ℃ of lower thermolysis 5min, these process repetitive coatings 30 levels, last sintering time under 350 ℃ is 20min, the rare-earth cerium doped Ti supported manganese dioxide electrode that obtains.
CN 201110098814 2011-04-20 2011-04-20 Method for treating printing and dyeing wastewater with rare earth cerium doped titanium-based manganese dioxide electrode Expired - Fee Related CN102229442B (en)

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CN102701333B (en) * 2012-05-31 2014-03-05 华南师范大学 Preparation method of Ce (cerium) doped titanium base SnO2 (stannic oxide) electrodes and metronidazole wastewater treatment method
CN104370348A (en) * 2014-10-14 2015-02-25 杭州广联新能源科技有限公司 Electrocatalytic oxidation coated electrode for treating oilfield wastewater and preparing method thereof
CN108677221B (en) * 2018-06-13 2020-06-16 昆明理工大学 Titanium-based β -MnO2Composite coating anode and preparation method thereof
CN109775813B (en) * 2019-03-13 2021-10-26 西安建筑科技大学 Composite intermediate layer for titanium-based oxide electrode, titanium-based oxide electrode and preparation method thereof

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CN1353088A (en) * 2000-11-09 2002-06-12 福建师范大学 Electrochemical process for treating waste dye liquid

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