CN108911106A - A method of utilizing graphene oxide wastewater degradation organic pollutant - Google Patents
A method of utilizing graphene oxide wastewater degradation organic pollutant Download PDFInfo
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- CN108911106A CN108911106A CN201810842634.XA CN201810842634A CN108911106A CN 108911106 A CN108911106 A CN 108911106A CN 201810842634 A CN201810842634 A CN 201810842634A CN 108911106 A CN108911106 A CN 108911106A
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- graphene oxide
- waste water
- organic pollutant
- degradation organic
- wastewater degradation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/02—Temperature
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses a kind of methods using graphene oxide wastewater degradation organic pollutant, include the following steps：The organic pollutant wastewater that graphene oxide waste water and COD are 50-10000mg/L mixes, graphene oxide waste water：The volume ratio of organic pollutant wastewater is 1：（10-20）, pH value range is 2.5-3.3, manganese ion concentration 20-60mg/L at this time；At a temperature of 15 DEG C -30 DEG C, oxidant is added；Duration of the reaction is one hour or more.Method of the invention is simple, and operation is easy, and solves the problems, such as the processing recycling of peracid, high manganese waste water, realizes the maximization of the utilization of resources；The acid and manganese ion in graphene oxide waste liquid are efficiently used, pollution sources can not only be eliminated, and being capable of degradable organic pollutant；Waste water reuse, it is more environmentally-friendly, improve environmental quality, organic sewage processing cost is low, and also avoids pollution and the waste of resource.
Description
Technical field
The present invention relates to technical field for the treatment of of organic waste, and in particular to a kind of organic using graphene oxide wastewater degradation
The method of pollutant.
Background technique
There are many enterprise for producing graphene oxide, and it is to use in the concentrated sulfuric acid that stone is added that Hummers method, which prepares graphene oxide,
Ink powder and sodium nitrate and potassium permanganate carry out oxidation reaction, then plus hydrogen peroxide is made in right amount to restore remaining oxidizing agent.It is producing
It can be inevitably generated waste water in the process, it is tight to contain the environmental pollutions such as sulfate, nitrate, manganese salt, suspended matter in waste water
The substance of weight, wherein manganese ion concentration is 400-600mg/L, sulphates content 2000-4500mg/L, and nitrate content is
1000-2000mg/L, PH 1-2.This is not only the waste of resource, can also have some impact on to social environment.Graphite at present
Alkene manufacturing enterprise mainly uses spent acid method of disposal the method for acid-base neutralization, needs to consume the alkali of equivalent, while also generating
A certain amount of salt.Removal for manganese ion generally uses coagulant sedimentation, such as the hydrogen of PB1 gene, 30% is added
Sodium oxide molybdena adjusts pH to 8-9.Which results in resources greatly to waste, and improves cost, does not meet contemporary environmental protection concept
It is required that.
High-level oxidation technology is to carry out active oxidation agent such as using metal ion such as iron ion, ferrous ion, manganese ion
Oxygen, hydrogen peroxide, persulfate improve the biodegradability of pollutant by oxidation.High-level oxidation technology includes electrochemical oxidation
Method, Ozonation and Fenton oxidation method etc..Fenton oxidation method is a kind of for waste water especially refractory wastewater
Effective advanced oxidation processes, principle be using hydrogen peroxide reacted with ferrous ion mixed solution generation hydroxyl radical free radical
Carboxylic acid, alcohol, esters oxidation of organic compounds are inorganic states by OH.
Summary of the invention
In order to solve the problems existing in the prior art, the present invention provides a kind of utilization graphene oxide wastewater degradation organic contamination
The method of object.Method of the invention is simple, and operation is easy, and solves the problems, such as the processing recycling of peracid, high manganese waste water, realizes money
The maximization that source utilizes；The acid and manganese ion in graphene oxide waste liquid are efficiently used, pollution sources, Er Qieneng can not only be eliminated
Enough degradable organic pollutants；Waste water reuse, it is more environmentally-friendly, improve environmental quality, organic sewage processing cost is low, but also keeps away
Pollution and the waste of resource are exempted from.
To achieve the goals above, the present invention uses following technical scheme：
A method of using graphene oxide wastewater degradation organic pollutant, include the following steps：
1）The organic pollutant wastewater that graphene oxide waste water and COD are 50-10000mg/L mixes, graphene oxide waste water：Have
The volume ratio of machine pollutant waste water is 1：（10-20）, pH value range is 2.5-3.3, manganese ion concentration 20-60mg/L at this time；
2）At a temperature of 15 DEG C -30 DEG C, oxidant is added；
3）Duration of the reaction is one hour or more.
Further, step（1）Middle graphene oxide waste water is the waste water that graphene oxide is prepared by Hummers method.
Further, step 2）Middle oxidant is one of hydrogen peroxide, persulfate and sulphite.
Preferably, in step 2）Middle addition Zero-valent Iron or ferrous ion keep Zero-valent Iron in solution dense as catalyst
Degree is 30-70 mg/L, ferrous ion concentration 10-25mg/L.After adding ferrous ion or Zero-valent Iron, degradation effect is bright
It is aobvious to improve.
Further, step 2）After middle addition hydrogen peroxide, make the concentration 10-30 mg/L of hydrogen peroxide in solution.
Further, step 2）After middle addition persulfate, make the concentration 0.2-3 mg/L of persulfate in solution.
Preferably, organic pollutant wastewater：Hydrogen peroxide：The mass ratio of graphene oxide GO waste water is 1:（1-3）：
（0.1-2）.
Preferably, organic pollutant wastewater：Persulfate：The mass ratio of GO waste water is 1:（0.02-0.3）：（0.1-
2）.
The beneficial effects of the invention are as follows：
（1）The present invention efficiently uses Hummers method and prepares acid and manganese ion in the waste liquid of graphene oxide, has reached waste again
The purpose utilized.
（2）The present invention prepares acid, manganese ion in the waste liquid of graphene oxide, additional hydrogen peroxide using Hummers method
Or persulfate constructs an advanced oxidation system, generates the extremely strong hydroxyl radical free radical of oxidability and potentiometric titrations, with
Quick chain reaction occurs for the organic pollutant in pollutant effluents, and organic pollutant is oxidized to non-selectivity CO2、H2O or
Mineral salt, without secondary pollution, very fast to the degradation rate of organic matter, degradation efficiency is high.
（3）Zero-valent Iron or ferrous ion enhancing activation effect can be also properly added during degradation of organic substances of the present invention,
Improve the ability of degradation of organic substances.
（4）Refuse reclamation of the present invention, organic sewage processing cost is low, and also avoids pollution and the waste of resource.
Detailed description of the invention
Fig. 1 is the schematic diagram of the method for the present invention.
Fig. 2 is the COD removal rate figure of 1 rhdamine B waste water of embodiment.
Fig. 3 is the COD removal rate figure of 2 bisphenol S waste water of embodiment.
Fig. 4 is the COD removal rate figure of 3 pharmaceutical wastewater of embodiment.
Specific embodiment
It is to be described in further detail to technical solution of the present invention below.It should be pointed out that embodiment is only to this
The specific descriptions of invention, and it is not construed as limitation of the invention.
Embodiment 1：
The graphene oxide GO waste water for taking 50mLHummers method to prepare, under conditions of 20 DEG C ± 2 DEG C, 500mLCOD, which is added, is
The rhdamine B waste water of [z1], pH value range is 2-5 at this time, and the hydrogen peroxide solution for adding 5ml2g/L reacts.?
It under the action of mechanical stirring, reacts one hour, measure the value [z2] of rhodamine B every 10min and calculates COD removal rate.
Embodiment 2：
The graphene oxide GO waste water for taking 50mLHummers method to prepare, under conditions of 20 DEG C ± 2 DEG C, 500mLCOD, which is added, is
The bisphenol S waste water of [z3], pH value range is 2-5 at this time, adds the Na of 1ml 1g/L2S2O8Solution reacts.In machinery
It under the action of stirring, reacts one hour, measure the COD value of bisphenol S waste water every 10min and calculates COD removal rate.
Embodiment 3：
The graphene oxide GO waste water for taking 50mLHummers method to prepare, under conditions of 20 DEG C ± 2 DEG C, 500mLCOD, which is added, is
The pharmaceutical wastewater of [z4], pH value range is 2-5 at this time, and the sodium sulfite solution for adding 2ml 1g/L reacts.In machinery
It under the action of stirring, reacts one hour, measure the COD value of pharmaceutical wastewater every 10min and calculates COD removal rate.
Testing result
The COD removal rate of rhdamine B waste water is as shown in Fig. 2, rhdamine B waste water after 1 hour in embodiment 1
COD removal rate is：80.7%, this illustrates that the method for the present invention can be effectively reduced the COD value of rhdamine B waste water, can be fast
Fast rhodamine B degradation.
In embodiment 2 bisphenol S waste water COD removal rate as shown in figure 3, after 1 hour bisphenol S waste water COD removal rate
For：75%, this illustrates that the method for the present invention can be effectively reduced the COD value of bisphenol S waste water, being capable of fast degradation bisphenol S.
The COD removal rate of 3 traditional Chinese medicine waste water of embodiment as shown in figure 4, after 1 hour pharmaceutical wastewater COD removal rate
For：79%, this illustrates that the method for the present invention can be effectively reduced the COD value of pharmaceutical wastewater, can be in fast degradation pharmaceutical wastewater
Organic matter.
Obviously, described embodiment is only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, it is obtained by those of ordinary skill in the art without making creative efforts every other
Embodiment should fall within the scope of the present invention.
Claims (6)
1. a kind of method using graphene oxide wastewater degradation organic pollutant, which is characterized in that include the following steps：
1）The organic pollutant wastewater that graphene oxide waste water and COD are 50-10000mg/L mixes, graphene oxide waste water：Have
The volume ratio of machine pollutant waste water is 1：（10-20）, pH value range is 2.5-3.3, manganese ion concentration 20-60mg/L at this time；
2）At a temperature of 15 DEG C -30 DEG C, oxidant is added；
3）Duration of the reaction is one hour or more.
2. a kind of method using graphene oxide wastewater degradation organic pollutant according to claim 1, feature exist
In the graphene oxide waste water is the waste water for preparing graphene oxide by Hummers method.
3. a kind of method using graphene oxide wastewater degradation organic pollutant according to claim 1, feature exist
In step 2）Middle oxidant is one of hydrogen peroxide, persulfate and sulphite.
4. a kind of method using graphene oxide wastewater degradation organic pollutant according to claim 1, in step（2）
Middle addition Zero-valent Iron or ferrous ion keep zeroth order concentration of iron 30-70 mg/L, ferrous ion in solution dense as catalyst
Degree is 10-25mg/L.
5. a kind of method using graphene oxide wastewater degradation organic pollutant according to claim 3, feature exist
In, be added hydrogen peroxide after, make the concentration 10-30 mg/L of hydrogen peroxide in solution.
6. a kind of method using graphene oxide wastewater degradation organic pollutant according to claim 3, feature exist
In, be added persulfate after, make the concentration 0.2-3 mg/L of persulfate in solution.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05345189A (en) * | 1992-06-12 | 1993-12-27 | Nippon Steel Corp | Method for treating organic halogen compound-containing waste water |
| CN105084507A (en) * | 2014-12-23 | 2015-11-25 | 郑州大学 | High-iron bauxite-hydrogen peroxide combined water treatment method |
| CN105330060A (en) * | 2015-11-05 | 2016-02-17 | 四川新能水处理工程有限公司 | Graphene wastewater treating and recycling system and treating and recycling technology thereof |
| CN106277649A (en) * | 2016-09-30 | 2017-01-04 | 中冶华天南京工程技术有限公司 | Class Fenton technology for paper waste pretreatment |
-
2018
- 2018-07-27 CN CN201810842634.XA patent/CN108911106A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05345189A (en) * | 1992-06-12 | 1993-12-27 | Nippon Steel Corp | Method for treating organic halogen compound-containing waste water |
| CN105084507A (en) * | 2014-12-23 | 2015-11-25 | 郑州大学 | High-iron bauxite-hydrogen peroxide combined water treatment method |
| CN105330060A (en) * | 2015-11-05 | 2016-02-17 | 四川新能水处理工程有限公司 | Graphene wastewater treating and recycling system and treating and recycling technology thereof |
| CN106277649A (en) * | 2016-09-30 | 2017-01-04 | 中冶华天南京工程技术有限公司 | Class Fenton technology for paper waste pretreatment |
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