CN105013500A - Heterogeneous Fenton catalyst for degrading azo dye wastewater as well as preparation method and application of heterogeneous Fenton catalyst - Google Patents

Heterogeneous Fenton catalyst for degrading azo dye wastewater as well as preparation method and application of heterogeneous Fenton catalyst Download PDF

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CN105013500A
CN105013500A CN201410164298.XA CN201410164298A CN105013500A CN 105013500 A CN105013500 A CN 105013500A CN 201410164298 A CN201410164298 A CN 201410164298A CN 105013500 A CN105013500 A CN 105013500A
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catalyst
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heterogeneous fenton
fenton catalyst
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CN105013500B (en
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范建伟
闵弘扬
姜序
李丹丹
陈旺源
陈敏骏
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Tongji University
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Abstract

The invention belongs to the technical fields of environment protection and catalyzing and relates to a heterogeneous Fenton catalyst for degrading azo dye wastewater as well as a preparation method and an application of the heterogeneous Fenton catalyst. The heterogeneous Fenton catalyst comprises the following components in percent by mole: 2-10% of CuO, 2-10% of MnOx, and 80-96% of TiO2. The heterogeneous Fenton catalyst prepared by the method disclosed by the invention is applied in degrading of the azo dyes, the efficiency is high, the hydrothermal stability is good, the regeneration cycling is realized, and no secondary pollution exists.

Description

Heterogeneous fenton catalyst of degrading azoic dye waste water and its production and use
Technical field
The invention belongs to environmental protection and catalysis technical field, heterogeneous fenton catalyst relating to degrading azoic dye waste water and its production and use.
Background technology
Azo dyes is dye the most frequently used at present, and the industrial dyestuff 50 ~ 70% used is all azo dyes, is widely used in weaving, leather, printing industry etc.Toxic and the bio-refractory of azo dyes, is difficult to remove with conventional method for treating water.Traditional physical treatment method, as absorption, filtration, coagulation etc., only can transfer to pollutant in other phases, can not thoroughly remove from water body.The removal and dye molecule can be degraded by high-level oxidation technology thoroughly.
Fenton reagent method is a kind of modal method in high-level oxidation technology.It utilizes iron ion and hydrogen peroxide as homogeneous catalyst, by producing the hydroxyl radical free radical of strong oxidizing property by organic molecule exhaustive oxidation.But the method Shortcomings part: first, reacts and could effectively carry out near pH=3; Secondly, in reactant liquor, meeting ferric remains ion, needs subsequent treatment to discharge.In order to overcome these shortcomings, heterogeneous catalysis obtains to be studied widely, with active carbon, aluminium oxide, molecular sieve for carrier, is synthesized out with the catalyst that the transition metal such as Cu, Mn, Fe are active component.
The pore-size distribution of mesoporous material is 2 ~ 50nm, is a kind of Porous materials between micropore and macropore.The pore-size distribution of mesoporous material can also provide the space of adsorbing and reacting for large molecule while maintaining high-specific surface area, and keeps good structural stability.Studied widely so mesoporous material obtains in recent years, as: mesoporous silicon, mesoporous carbon and mesoporous metallic oxide material.TiO 2be a kind of material of nontoxic, wide material sources, often used by as catalyst carrier.Himself just has catalytic performance.Mesoporous TiO 2the advantage of itself can be inherited, the little shortcoming of specific area can be overcome again, thus become a desirable catalyst carrier.
Therefore, with mesoporous TiO 2for carrier, loaded Cu and Mn thereon, the catalyst of synthesizing high specific surface area, high-activity component load capacity, high hydrothermal stability and high catalytic activity is also applied to organic degraded in water body and is significant.
Summary of the invention
The object of the invention is to the defect for overcoming prior art and heterogeneous fenton catalyst that a kind of degrading azoic dye waste water is provided and its production and use.
For achieving the above object, the present invention is by the following technical solutions:
For a heterogeneous fenton catalyst for degrading azoic dye waste water, comprise the component of following molar percentage:
CuO 2～10％，
MnO x2～10％，
TiO 280～96％。
Wherein MnO xmiddle x=2, one or more in 3/2 or 8/5.
The grain diameter of the heterogeneous fenton catalyst of described degrading azoic dye waste water is 4 ~ 8nm, specific area 100 ~ 250m 2/ g, pore volume 0.15 ~ 0.30mL/g.This catalyst belongs to the mesoporous material in nano material, is orderly two-dimentional hexagonal hole structure.
A preparation method for above-mentioned catalyst, comprises the following steps:
(1) add surfactant, hydrochloric acid and sulfuric acid in ethanol, be uniformly mixed;
(2) in said mixture, add isopropyl titanate, mix;
(3) said mixture is transferred in culture dish, standing, aging, obtain white powder;
(4) white powder calcining is obtained mesoporous TiO 2carrier;
(5) by mesoporous TiO 2carrier joins in the mixed solution of copper nitrate and manganese nitrate, stirs and fully mixes;
(6) filter said mixture, be separated and obtain solid matter, after oven dry, roasting, obtain catalyst.
Described surfactant is three block surface activating agent P123, and sulfuric acid is the sulfuric acid of 45% concentration, and hydrochloric acid is concentrated hydrochloric acid.
In described step (1), the mass ratio of sulfuric acid, hydrochloric acid, surfactant and ethanol is 1:(3 ~ 5): (1 ~ 3): (30 ~ 60) are uniformly mixed 2 ~ 5 hours at 20 ~ 50 DEG C.
In described step (2), the mass ratio of isopropyl titanate and surfactant is 3:(1 ~ 2); 10 ~ 20 hours are uniformly mixed at 20 ~ 50 DEG C.
In described step (3), mixture is statically placed in temperature 40 DEG C, humidity is 40 ~ 60% times 1 ~ 3 day, then at 100 DEG C aging 1 ~ 3 day.
In described step (4), first 350 ~ 550 DEG C of roastings 3 ~ 5 hours in a nitrogen atmosphere, then 350 ~ 450 DEG C of roastings 5 hours in air atmosphere.
In described step (5), mesoporous TiO 2carrier is stirring at normal temperature fully mixing in 6 hours in the mixed solution of copper nitrate and manganese nitrate, wherein TiO 2with solution quality than being 1:(50 ~ 100); In described copper nitrate and the mixed solution of manganese nitrate, copper nitrate, manganese nitrate concentration are respectively 0.5-1.0 mol/L.
In described step (6), dry 12 hours at 105 DEG C, then roasting 3 ~ 5 hours at 350 ~ 450 DEG C.
Utilize a method for above-mentioned catalyst degradation azo dye wastewater, comprise the following steps:
(a), azo dye wastewater pH is adjusted to 3 ~ 7, heat in a reservoir and maintain 30 ~ 90 DEG C;
(b), proper catalyst and hydrogen peroxide are joined in waste liquid, and stir with the speed of 300 ~ 700 revs/min, the ratio wherein between the dosage of catalyst and hydrogen peroxide and organic concentration three is about (2 ~ 5): (20 ~ 40): 1;
(c), after 0.5 ~ 3 hour, reaction terminate after catalyst filtration is out reclaimed.
The present invention has following beneficial effect:
Heterogeneous fenton catalyst that the invention provides degrading azoic dye waste water and its production and use.The cost of material of Kaolinite Preparation of Catalyst is low, can recycling utilization, non-secondary pollution.Its preparation method is simple to operate, with low cost.The features such as it is large that the catalyst that a process for preparing has specific area, and activity component load quantity is high, good dispersion, and hydrothermal stability is high, the use of energy regeneration cycle.Mesoporous TiO2 carrier in the present invention has high-specific surface area, and himself just has certain catalytic action; In the duct that it is interconnected, organic matter can free diffusing, is beneficial to the carrying out of reaction.Catalyst of the present invention has very high catalytic activity in the reaction of degrade azo dyestuff, and 70 DEG C time, degraded concentration is the acid red solution of 200mg/L, can reach the clearance of 99%.
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be further described.
Embodiment 1
(1) add surfactant, hydrochloric acid and sulfuric acid in ethanol, and be fully uniformly mixed 2 hours at 20 DEG C, wherein the mass ratio of sulfuric acid, hydrochloric acid, surfactant and ethanol is 1:3:1:30;
(2) in said mixture, add isopropyl titanate, and be uniformly mixed 10 hours at 20 DEG C, wherein the mass ratio of isopropyl titanate and surfactant is 3:1;
(3) said mixture is transferred in culture dish, to be statically placed under the environmental condition of 40 DEG C and 40% humidity volatilization 1 day, then at 100 DEG C aging 1 day;
(4) gained white powder first 350 DEG C of roastings 3 hours in a nitrogen atmosphere, then 350 DEG C of roastings 3 hours in air atmosphere, obtain mesoporous TiO 2carrier;
(5) by mesoporous TiO 2join in the copper nitrate and manganese nitrate solution that concentration is 0.5mol/L, stirring at normal temperature fully mixing in 6 hours, wherein TiO 2with solution quality than being 1:50;
(6) separated by the solid matter in said mixture by filtering, and dry 12 hours at 105 DEG C, then roasting 5 hours at 350 DEG C, obtains described catalyst.
The physical parameter of catalyst is: grain diameter is 4 ~ 8nm, specific area 100 ~ 250m 2/ g, pore volume 0.15 ~ 0.30mL/g.The mol ratio of Cu, Mn, Ti element is 2%:2%:96%, and wherein Mn is MnO 2, Mn 2o 3or Mn 5o 8in one or more.70 DEG C time, degraded concentration is the acid red solution of 200mg/L, and can reach the clearance of 95%, concrete steps are as follows:
A. azo dye wastewater pH is adjusted to 7, heats in a reservoir and maintain 70 DEG C;
B. proper catalyst and hydrogen peroxide are joined in waste liquid, and stir with the speed of 300 revs/min, wherein catalyst and hydrogen peroxide dosage are respectively 1g/L and 8g/L;
C., after 1 hour, after reaction terminates, catalyst filtration is out reclaimed.
Embodiment 2
(1) add surfactant, hydrochloric acid and sulfuric acid in ethanol, and be fully uniformly mixed 2 hours at 20 DEG C, wherein the mass ratio of sulfuric acid, hydrochloric acid, surfactant and ethanol is 1:5:3:60;
(2) in said mixture, add isopropyl titanate, and be uniformly mixed 10 hours at 20 DEG C, wherein the mass ratio of isopropyl titanate and surfactant is 3:2;
(3) said mixture is transferred in culture dish, to be statically placed under the environmental condition of 40 DEG C and 40% humidity volatilization 1 day, then at 100 DEG C aging 1 day;
(4) gained white powder first 350 DEG C of roastings 3 hours in a nitrogen atmosphere, then 350 DEG C of roastings 3 hours in air atmosphere, obtain mesoporous TiO2 carrier;
(5) by mesoporous TiO 2join in the copper nitrate and manganese nitrate solution that concentration is 1.0mol/L, stirring at normal temperature fully mixing in 6 hours, wherein TiO 2with solution quality than being 1:100;
(6) separated by the solid matter in said mixture by filtering, and dry 12 hours at 105 DEG C, then roasting 5 hours at 350 DEG C, obtains described catalyst.
The physical parameter of catalyst is: grain diameter is 4 ~ 8nm, specific area 100 ~ 250m 2/ g, pore volume 0.15 ~ 0.30mL/g.The mol ratio of Cu, Mn, Ti element is 10:10:80, and wherein Mn is MnO 2, Mn 2o 3or Mn 5o 8in one or more.70 DEG C time, degraded concentration is the acid red solution of 200mg/L, and can reach the clearance of 99%, concrete steps are as follows:
A. azo dye wastewater pH is adjusted to 3, heats in a reservoir and maintain 70 DEG C;
B. proper catalyst and hydrogen peroxide are joined in waste liquid, and stir with the speed of 500 revs/min, wherein catalyst and hydrogen peroxide dosage are respectively 1g/L and 10g/L;
C., after 2 hours, after reaction terminates, catalyst filtration is out reclaimed.
Embodiment 3
(1) add surfactant, hydrochloric acid and sulfuric acid in ethanol, and be fully uniformly mixed 2 hours at 20 DEG C, wherein the mass ratio of sulfuric acid, hydrochloric acid, surfactant and ethanol is 1:4:2:40;
(2) in said mixture, add isopropyl titanate, and be uniformly mixed 10 hours at 20 DEG C, wherein the mass ratio of isopropyl titanate and surfactant is 3:1.5;
(3) said mixture is transferred in culture dish, to be statically placed under the environmental condition of 40 DEG C and 40% humidity volatilization 1 day, then at 100 DEG C aging 1 day;
(4) gained white powder first 350 DEG C of roastings 3 hours in a nitrogen atmosphere, then 350 DEG C of roastings 3 hours in air atmosphere, obtain mesoporous TiO 2carrier;
(5) by appropriate mesoporous TiO 2join in the copper nitrate and manganese nitrate solution that concentration is 0.5mol/L, stirring at normal temperature fully mixing in 6 hours, wherein TiO 2with solution quality than being 1:70;
(6) separated by the solid matter in said mixture by filtering, and dry 12 hours at 105 DEG C, then roasting 5 hours at 350 DEG C, obtains described catalyst.
The physical parameter of catalyst is: grain diameter is 4 ~ 8nm, specific area 100 ~ 250m 2/ g, pore volume 0.15 ~ 0.30mL/g.The mol ratio of Cu, Mn, Ti element is 5:5:90, and wherein Mn is MnO 2, Mn 2o 3or Mn 5o 8in one or more.50 DEG C time, degraded concentration is the acid red solution of 200mg/L, and can reach the clearance of 90%, concrete steps are as follows:
A. azo dye wastewater pH is adjusted to 7, heats in a reservoir and maintain 50 DEG C;
B. proper catalyst and hydrogen peroxide are joined in waste liquid, and stir with the speed of 700 revs/min, wherein catalyst and hydrogen peroxide dosage are respectively 0.6g/L and 12g/L;
C., after 0.5 hour, after reaction terminates, catalyst filtration is out reclaimed.
Above-mentioned is can understand and apply the invention for ease of those skilled in the art to the description of embodiment.Person skilled in the art obviously easily can make various amendment to these embodiments, and General Principle described herein is applied in other embodiments and need not through performing creative labour.Therefore, the invention is not restricted to embodiment here, those skilled in the art, according to announcement of the present invention, do not depart from improvement that scope makes and amendment all should within protection scope of the present invention.

Claims (10)

1. for a heterogeneous fenton catalyst for degrading azoic dye waste water, it is characterized in that: the component comprising following molar percentage:
CuO 2～10％，
MnO x2～10％，
TiO 280～96％。
2. heterogeneous fenton catalyst according to claim 1, is characterized in that: above-mentioned MnO xmiddle x=2,3/2 or 8/5;
Or the grain diameter of the heterogeneous fenton catalyst of described degrading azoic dye waste water is 4 ~ 8nm, specific area 100 ~ 250m 2/ g, pore volume 0.15 ~ 0.30mL/g.
3. the preparation method of arbitrary described heterogeneous fenton catalyst in claim 1 or 2, is characterized in that: comprise the following steps:
(1) add surfactant, hydrochloric acid and sulfuric acid in ethanol, be uniformly mixed;
(2) in said mixture, add isopropyl titanate, mix;
(3) said mixture is transferred in culture dish, standing, aging, obtain white powder;
(4) white powder calcining is obtained mesoporous TiO 2carrier;
(5) by mesoporous TiO 2carrier joins in the mixed solution of copper nitrate and manganese nitrate, stirs and fully mixes;
(6) filter said mixture, be separated and obtain solid matter, after oven dry, roasting, obtain heterogeneous fenton catalyst.
4. preparation method according to claim 3, is characterized in that: described surfactant is three block surface activating agent P123, and sulfuric acid is the sulfuric acid of 45% concentration, and hydrochloric acid is concentrated hydrochloric acid.
5. preparation method according to claim 3, it is characterized in that: in described step (1), the mass ratio of sulfuric acid, hydrochloric acid, surfactant and ethanol is 1:(3 ~ 5): (1 ~ 3): (30 ~ 60) are uniformly mixed 2 ~ 5 hours at 20 ~ 50 DEG C;
Or in described step (2), the mass ratio of isopropyl titanate and surfactant is 3:(1 ~ 2); 10 ~ 20 hours are uniformly mixed at 20 ~ 50 DEG C.
6. preparation method according to claim 3, is characterized in that: in described step (3), mixture is statically placed in temperature 40 DEG C, humidity is 40 ~ 60% times 1 ~ 3 day, then at 100 DEG C aging 1 ~ 3 day.
7. preparation method according to claim 3, is characterized in that: in described step (4), first 350 ~ 550 DEG C of roastings 3 ~ 5 hours in a nitrogen atmosphere, then 350 ~ 450 DEG C of roastings 5 hours in air atmosphere.
8. preparation method according to claim 3, is characterized in that: in described step (5), mesoporous TiO 2carrier is stirring at normal temperature fully mixing in 6 hours in the mixed solution of copper nitrate and manganese nitrate, wherein TiO 2with solution quality than being 1:(50 ~ 100); In described copper nitrate and the mixed solution of manganese nitrate, copper nitrate, manganese nitrate concentration are respectively 0.5-1.0mol/L.
9. preparation method according to claim 3, is characterized in that: in described step (6), dries 12 hours at 105 DEG C, then roasting 3 ~ 5 hours at 350 ~ 450 DEG C.
10. utilize a method for arbitrary described heterogeneous fenton catalyst degrading azoic dye waste water in claim 1 or 2, it is characterized in that: comprise the following steps:
(a), azo dye wastewater pH is adjusted to 3 ~ 7, heat in a reservoir and maintain 30 ~ 90 DEG C;
(b), catalyst and hydrogen peroxide are joined in waste liquid, and stir with the speed of 300 ~ 700 revs/min, the ratio wherein between the dosage of catalyst and hydrogen peroxide and organic concentration three is about (2 ~ 5): (20 ~ 40): 1;
(c), after 0.5 ~ 3 hour, reaction terminate after catalyst filtration is out reclaimed.
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CN105396578A (en) * 2015-12-09 2016-03-16 哈尔滨工业大学 A preparing method of a doped type nanometer MnO2-CeO2/Al2O3 catalyst and applications of the catalyst
CN108671937A (en) * 2018-05-16 2018-10-19 华侨大学 A kind of preparation method and applications of copper-manganese composite oxide catalysts
CN110449159A (en) * 2018-05-08 2019-11-15 沈阳药科大学 A kind of fenton catalyst Fe3O4-CeO2/ AC and its preparation method and application
CN111111664A (en) * 2019-12-22 2020-05-08 华东理工大学 Catalyst for Fenton-like continuous treatment of low-concentration organic wastewater and preparation method and application thereof
CN111151250A (en) * 2019-12-30 2020-05-15 肇庆学院 Preparation method of fluorescent copper nanocluster-carbon composite catalyst

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Publication number Priority date Publication date Assignee Title
CN105344360A (en) * 2015-12-09 2016-02-24 哈尔滨工业大学 Preparation method and application of doping type nanometer MnO<2>-CuO/Al<2>O<3> catalyst
CN105396578A (en) * 2015-12-09 2016-03-16 哈尔滨工业大学 A preparing method of a doped type nanometer MnO2-CeO2/Al2O3 catalyst and applications of the catalyst
CN110449159A (en) * 2018-05-08 2019-11-15 沈阳药科大学 A kind of fenton catalyst Fe3O4-CeO2/ AC and its preparation method and application
CN108671937A (en) * 2018-05-16 2018-10-19 华侨大学 A kind of preparation method and applications of copper-manganese composite oxide catalysts
CN111111664A (en) * 2019-12-22 2020-05-08 华东理工大学 Catalyst for Fenton-like continuous treatment of low-concentration organic wastewater and preparation method and application thereof
CN111151250A (en) * 2019-12-30 2020-05-15 肇庆学院 Preparation method of fluorescent copper nanocluster-carbon composite catalyst

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