CN102976476A - Ozonization water treatment method by taking copper/silver composite material as catalyst - Google Patents
Ozonization water treatment method by taking copper/silver composite material as catalyst Download PDFInfo
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- CN102976476A CN102976476A CN2012105549976A CN201210554997A CN102976476A CN 102976476 A CN102976476 A CN 102976476A CN 2012105549976 A CN2012105549976 A CN 2012105549976A CN 201210554997 A CN201210554997 A CN 201210554997A CN 102976476 A CN102976476 A CN 102976476A
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Abstract
The invention provides an ozonization water treatment method by taking a copper/silver composite material as a catalyst. The copper/silver composite material is added into an ozonization water treatment system with waste water containing phenol and is used for promoting degrading of ozone on phenol organic pollutants. On the basis, the invention provides a novel ozonization water treatment method. The method belongs to the technical field of water treatment and environment catalysis. The copper/silver composite material has the characteristics of high cleaning property and high stability and can be used in a relatively wide initial pH range (4 to 8); and the copper/silver composite material has a wide prospect in ozonization water treatment.
Description
Technical field
The present invention proposes a kind of ozonization water treatment method take copper/silver composite material as catalyzer and reduces the water pollution, belongs to environmental catalysis and water treatment field.
Background technology
China's water resources is abundant, but the occupancy volume per person is lower.Along with expanding economy, day by day serious shortage of water resources and water quality security have become the great resource environment problem in the world today.In every year, a large amount of organic waste waters are discharged into environment.If these organic waste waters are recycled after processing, not only can effectively improve environment, can also alleviate global insufficient water.
Because ozone has higher redox potential and do not have secondary pollution in water, the application of ozone in water treatment is more and more extensive.From beginning for sterilization, finally except algae, deodorizing, decolouring, removal organism etc.But along with ozone constantly uses, it is found that the use ozonize can not degradable organism separately at low dosage with in the short period of time.Therefore, the introducing of catalyzer just becomes imperative.
Catalytic ozonation is that the absorption of the oxidisability of ozone and catalyzer, catalysis characteristics are combined, and can effectively solve the incomplete problem of organic pollutant degradation.Catalytic ozonation generally is divided into homogeneous catalysis and heterogeneous catalyst.Homogeneous catalyst commonly used is transition metal ion, mainly contains Fe
2+, Mn
2+, Ni
2+, Co
2+, Cd
2+, Cu
2+, Ag
+, Zn
2+Deng.The effect of homogeneous catalysis organic pollutant is better than independent ozonize, but homogeneous catalyst easily runs off in reaction process, is difficult to after reaction finishes separate and recycle, the problem that exists follow-up metal ion to remove, cause processing cost to increase, and the metal ion of introducing is influential to water quality.If the homogeneous catalyst ion that remains in the water can not effectively be removed, will cause metal ion pollution to water body, this will greatly reduce the recycling of processing rear water and be worth.
For the homogeneous catalysis ozonize in water treatment catalyzer can not Reusability, the easy shortcoming such as kish ion in the water, exploitation can recycle, be easy to moisture from catalyzer become a study hotspot of catalytic ozonation water treatment field.And heterogeneous catalytic ozonation since its use be that solid catalyst has reduced secondary pollution to a certain extent, in the limited water treatment field of homogeneous catalysis, particularly the removal of hardly degraded organic substance has broad application prospects in the tap water.The selection of catalyzer is extremely important in this course, researchs and develops the degradation efficiency that suitable, efficient catalyzer can improve catalytic ozonation greatly.
Summary of the invention
The object of the present invention is to provide a kind of efficient matrix material, and its ozonization water treatment method is provided, and then improve catalytic ozonation in the actual application value of water treatment field.Purpose of the present invention can be achieved through the following technical solutions:
(1) preparation of copper/silver composite material: 30ml ethylene glycol joined fill 10mmol CuSO
45H
2In the container of O, dissolve under the magnetic agitation, then add 20mL water in mentioned solution, be transferred in the 250mL flask after continuing to stir 10min, slowly be warming up to 80 ℃, the speed with 3.3mL/min under this temperature dropwise adds 0.2mol/LNaCO
3Solution 100mL, after continuing to stir 1h and leaving standstill 1h, washing, ethanol are washed successively, 100 ℃ of dryings, the pressed powder that obtains is the copper precursor.Accurately this copper precursor of weighing 0.4g is in the 50mL beaker, the formaldehyde, the 0.2g Silver Nitrate that add respectively 30ml ethylene glycol, 1mL 37% under the magnetic agitation, transfer them in the 50mL reactor after continuing to stir 10min, 200 ℃ of lower hydro-thermal reaction 6h, after naturally cooling to room temperature, transfer in the beaker ethanol and wash, 80 ℃ of dryings, the pressed powder that obtains is copper/silver composite material.
(2) ozonization water treatment: synthetic matrix material is joined in the waste water, pass into ozone under stirring, beginning catalyzing oxidizing degrading organic pollutant.
In experimentation, we find to add the amount of catalyzer and the mass ratio of the waste water of processing is 0.001, and temperature of reaction can reach preferably catalytic effect in the time of 25 ℃.
Distinguishing feature of the present invention
(1) there is adsorption in phenol hardly on copper/silver composite material, and its katalysis mainly promotes the decomposition of ozone molecule from catalyst surface, and then improves degradation efficiency.
(2) copper/silver composite material good stability in a wider initial pH scope (4-8), all has preferably catalytic activity.
(3) copper/silver composite material building-up process cleaning, energy consumption is low, for its practical application provides important guarantee.
Description of drawings
Fig. 1 is embodiment 1,2, the SEM photo of 3 products obtained therefroms;
Fig. 2 is embodiment 1,2, the XRD figure spectrum of 3 products obtained therefroms;
Fig. 3 be among the embodiment 4 phenol with the concentration curve of ozonize time, (a) line is independent ozonize (catalyst-free), (b) line is Cu-HCHO material catalytic ozonation among the embodiment 1, (c) line is Cu-Ag material catalytic ozonation among the embodiment 2, and (d) line is Cu-Ag-HCHO material catalytic ozonation among the embodiment 3;
Fig. 4 be among the embodiment 5 phenol with the concentration curve of ozonize time, (a) line is independent ozonize (pH=4.06), (b) line is Cu-Ag-HCHO material catalytic ozonation (pH=4.06) among the embodiment 3, (c) line is independent ozonize (pH=6.17), (d) line is Cu-Ag-HCHO material catalytic ozonation (pH=6.17) among the embodiment 3, (e) line be independent ozonize (pH=7.91) (f) line be Cu-Ag-HCHO material catalytic ozonation (pH=7.91) among the embodiment 3.
Embodiment
For more specific description method of the present invention, the below provides embodiments of the invention, but application of the present invention is not limited to this.
Embodiment 1
30ml ethylene glycol joined fill 10mmol CuSO
45H
2In the container of O, dissolve under the magnetic agitation, then add 20mL water in mentioned solution, be transferred in the 250mL flask after continuing to stir 10min, slowly be warming up to 80 ℃, the speed with 3.3mL/min under this temperature dropwise adds 0.2mol/L NaCO
3Solution 100mL, after continuing to stir 1h and leaving standstill 1h, washing, ethanol are washed successively, 100 ℃ of dried overnight, the pressed powder that obtains is the copper precursor.Accurately this copper precursor of weighing 0.4g is in the 50mL beaker, the formaldehyde that adds respectively 30ml ethylene glycol and 1mL 37% under the magnetic agitation, transfer them in the 50mL reactor after continuing to stir 10min, 200 ℃ of lower hydro-thermal reaction 6h, after naturally cooling to room temperature, transfer in the beaker ethanol and wash, 80 ℃ of dried overnight, the pressed powder that obtains after the grinding is the Cu-HCHO matrix material.Its SEM photo is seen (a) among Fig. 1, and the XRD figure spectrum is seen (a) among Fig. 2.
Embodiment 2
30ml ethylene glycol joined fill 10mmol CuSO
45H
2In the container of O, dissolve under the magnetic agitation, then add 20mL water in mentioned solution, be transferred in the 250mL flask after continuing to stir 10min, slowly be warming up to 80 ℃, the speed with 3.3mL/min under this temperature dropwise adds 0.2mol/L NaCO
3Solution 100mL, after continuing to stir 1h and leaving standstill 1h, washing, ethanol are washed successively, 100 ℃ of dried overnight, the pressed powder that obtains is the copper precursor.Accurately this copper precursor of weighing 0.4g is in the 50mL beaker, add respectively 30ml ethylene glycol and 0.2g Silver Nitrate under the magnetic agitation, transfer them in the 50mL reactor after continuing to stir 10min, 200 ℃ of lower hydro-thermal reaction 6h, after naturally cooling to room temperature, transfer in the beaker ethanol and wash, 80 ℃ of dried overnight, the pressed powder that obtains after the grinding is the Cu-Ag matrix material.Its SEM photo is seen (b) among Fig. 1, and the XRD figure spectrum is seen (b) among Fig. 2.
Embodiment 3
30ml ethylene glycol joined fill 10mmol CuSO
45H
2In the container of O, dissolve under the magnetic agitation, then add 20mL water in mentioned solution, be transferred in the 250mL flask after continuing to stir 10min, slowly be warming up to 80 ℃, the speed with 3.3mL/min under this temperature dropwise adds 0.2mol/L NaCO
3Solution 100mL, after continuing to stir 1h and leaving standstill 1h, washing, ethanol are washed successively, 100 ℃ of dried overnight, the pressed powder that obtains is the copper precursor.Accurately this copper precursor of weighing 0.4g is in the 50mL beaker, the formaldehyde, the 0.2g Silver Nitrate that add respectively 30ml ethylene glycol, 1mL37% under the magnetic agitation, transfer them in the 50mL reactor after continuing to stir 10min, 200 ℃ of lower hydro-thermal reaction 6h, after naturally cooling to room temperature, transfer in the beaker ethanol and wash, 80 ℃ of dried overnight, the pressed powder that obtains after the grinding is the Cu-Ag-HCHO matrix material.Its SEM photo is seen (c) among Fig. 1, and the XRD figure spectrum is seen (c) among Fig. 2.
Containing initial phenol concentration at 200ml is 300mg L
-1Simulated wastewater in, add different material 0.20g, start stirring, under 25 ℃ of temperature of reaction, pass into ozone, oxygen flow 21mL/min, the concentration of phenol under the record different time.The result respectively as shown in Figure 3.
(a) line is independent ozonize (catalyst-free) among Fig. 3, (b) line is Cu-HCHO material catalytic ozonation among the embodiment 1, (c) line is Cu-Ag material catalytic ozonation among the embodiment 2, and (d) line is Cu-Ag-HCHO material catalytic ozonation among the embodiment 3;
Embodiment 5
Be 300mg L at 200ml, starting point concentration
-1Phenol solution in, adjust its initial pH and be respectively 4.06,6.17 and 7.91, add Cu-Ag-HCHO matrix material 0.20g, start stirring, under 25 ℃ of temperature of reaction, pass into ozone, oxygen flow 21mL/min, the concentration of phenol under the record different time.The result respectively as shown in Figure 4.
(a) line is independent ozonize (pH=4.06) among Fig. 4, (b) line is Cu-Ag-HCHO material catalytic ozonation (pH=4.06) among the embodiment 3, (c) line is independent ozonize (pH=6.17), (d) line is Cu-Ag-HCHO material catalytic ozonation (pH=6.17) among the embodiment 3, (e) line be independent ozonize (pH=7.91) (f) line be Cu-Ag-HCHO material catalytic ozonation (pH=7.91) among the embodiment 3.
Claims (1)
1. ozonization water treatment method take copper/silver composite material as catalyzer is characterized in that implementation step is as follows:
(1) preparation of copper/silver composite material: 30ml ethylene glycol joined fill 10mmol CuSO
45H
2In the container of O, dissolve under the magnetic agitation, then add 20mL water in mentioned solution, be transferred in the 250mL flask after continuing to stir 10min, slowly be warming up to 80 ℃, the speed with 3.3mL/min under this temperature dropwise adds 0.2mol/LNaCO
3Solution 100mL, after continuing to stir 1h and leaving standstill 1h, washing, ethanol are washed successively, 100 ℃ of dryings, the pressed powder that obtains is the copper precursor.Accurately this copper precursor of weighing 0.4g is in the 50mL beaker, the formaldehyde, the 0.2g Silver Nitrate that add respectively 30ml ethylene glycol, 1mL 37% under the magnetic agitation, transfer them in the 50mL reactor after continuing to stir 10min, 200 ℃ of lower hydro-thermal reaction 6h, after naturally cooling to room temperature, transfer in the beaker ethanol and wash, 80 ℃ of dryings, the pressed powder that obtains after the grinding is copper/silver composite material.
(2) ozonization water treatment: synthetic matrix material is joined in the waste water, pass into ozone under stirring, beginning catalyzing oxidizing degrading organic pollutant.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109896693A (en) * | 2017-12-08 | 2019-06-18 | 中国石油化工股份有限公司 | A kind of sewage treatment process that nitrogen and COD is removed in depth |
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| US5192452A (en) * | 1988-07-12 | 1993-03-09 | Nippon Shokubai Kagaku Kogyo, Co., Ltd. | Catalyst for water treatment |
| CN1546397A (en) * | 2003-12-09 | 2004-11-17 | 哈尔滨工业大学 | Method for honeycomb ceramics catalytic ozonization decomposition of organic matters in water |
| CN1868916A (en) * | 2006-06-07 | 2006-11-29 | 哈尔滨工业大学 | Catalytic ozonization water treatment method |
| CN102451711A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Industrial wastewater treatment catalyst and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109896693A (en) * | 2017-12-08 | 2019-06-18 | 中国石油化工股份有限公司 | A kind of sewage treatment process that nitrogen and COD is removed in depth |
| CN109896693B (en) * | 2017-12-08 | 2021-08-06 | 中国石油化工股份有限公司 | Sewage treatment process for deeply removing nitrogen and COD |
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