CN106829873B - The method that ferrous iron-silicic acid complex activate molecular oxygen generates hydrogen peroxide in situ - Google Patents
The method that ferrous iron-silicic acid complex activate molecular oxygen generates hydrogen peroxide in situ Download PDFInfo
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- CN106829873B CN106829873B CN201710125212.6A CN201710125212A CN106829873B CN 106829873 B CN106829873 B CN 106829873B CN 201710125212 A CN201710125212 A CN 201710125212A CN 106829873 B CN106829873 B CN 106829873B
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- free radical
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/027—Preparation from water
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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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
- C02F2101/36—Organic compounds containing halogen
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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
- C02F2305/026—Fenton's reagent
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Abstract
The invention discloses the method that a kind of ferrous iron-silicic acid complex activate molecular oxygen generates hydrogen peroxide in situ, the silicate in system forms complex with ferrous ion, forms the stronger ferrous iron-siliceous species of reducing power so that O2One-electron reduction occurs, generates ultra-oxygen anion free radical (O2 ‑), ultra-oxygen anion free radical is using being further reduced to H2O2.Simultaneously as H2O2It is existed simultaneously with ferrous coordination compound, Fenton effects can be generated, generate a large amount of hydroxyl radical free radical (OH), hydroxyl radical free radical, almost can be without selectively degradation and mineralising organic pollution as a kind of strong oxidizer.The use of silicate will not bring secondary pollution, will not compete hydroxyl radical free radical with organic matter.Ferrous ion can derive from natural water, or the divalent iron salt by being manually added in solution generates, or be occurred by Zero-valent Iron and reactant aqueous solution, can also be electrolysed and be generated by iron anode.The present invention has wide practical use in fields such as environment remediation, water process.
Description
Technical field
The invention belongs to field of environment protection, and in particular to a kind of ferrous iron-silicic acid complex activate molecular oxygen original position generation peroxide
Change the method for treating water of hydrogen.
Background technology
Hydrogen peroxide is compound that is a kind of while having oxidation and reduction characteristic, encounters oxidizing substance, display reduction
Property；Reducing substances are encountered, show certain oxidisability.Simultaneously as the oxidation product of hydrogen peroxide is oxygen, also originate in
Object is water, so being considered as a kind of green, non-secondary pollution chemicals, is widely used in production and sphere of life.
Chemical field, hydrogen peroxide can be used for the synthesis material of chemicals；In field of environment protection, hydrogen peroxide can generate disinfection effect
It answers, oxidation effect, while Fenton effects can be generated with ferrous ion (hydroxyl radical free radical of formation can generate strong
Advanced oxidation effect)；In social life field, the weak solution of hydrogen peroxide be used to sterilize and decolourize etc..
The mode of production of industrial hydrogen peroxide is mainly ethyl hydrazine method, and mass concentration can be generated by this method
30% hydrogen peroxide.In actual application, there is the security risk of corrosion and explosion using the hydrogen peroxide of high concentration.Cause
This, fabricated in situ or generation hydrogen peroxide are more safe and reliable, become the first choices of various environmental protection applications.So-called fabricated in situ,
Refer to hydrogen peroxide directly being generated by physical chemistry or biological respinse in the place of application, rather than pass through additional peroxidating
The mode of hydrogen generates.The hydrogen peroxide of fabricated in situ low concentration not will produce security risk, meanwhile, iron ion or other
Under the conditions of transition-metal catalyst is existing, Fenton advanced oxidation effects can be generated, for sewage disposal, oxidation sterilizing,
Sludge dewatering, environment remediation etc..Therefore, seek cost savings, easy-to-use hydrogen peroxide in situ generation method, be always
The hot fields of field of environment protection.
Currently, in situ generate there are many hydrogen peroxide, it can substantially be divided into electrochemical process and non-electrochemical process,
Basic principle is all to molecular oxygen (O2) restored, generate hydrogen peroxide.Wherein electrochemical process mainly uses cathode also
Former process (gas-diffusion electrode, graphite and carbon cathode, metal foam cathode etc.), the electronics of cathode is directly passed to O2, generate
Hydrogen peroxide.Non-electrochemical mode includes mainly electronation oxygen molecule, enzymatic reduction oxygen molecule and micro-reduction oxygen
Son generates the several ways of hydrogen peroxide.Wherein, reduction is carried out to oxygen molecule using electronation substance and generates hydrogen peroxide,
It is a new phenomenon of discovered in recent years, also known as Activation of Molecular Oxygen method.It has now been found that, the change with Activation of Molecular Oxygen effect
Learn the complex etc. that reducing substances include mainly zeroth order ferrous metal, the sulfide of iron and ferrous iron.Wherein, Zero-valent Iron and iron
The concentration of hydrogen peroxide that sulfide generates is not high, and since Zero-valent Iron and iron sulfide are the different-phase catalysts of strong reducing property, makes
The hydrogen peroxide that must be generated lacks environmentally friendly application value.Zero-valent Iron ferrous coordination compound includes mainly ferrous iron-ethylenediamine tetra-acetic acid
Complex (Fe (II)-EDTA) and ferrous-four polyphosphoric acids etc., these types of complex have stronger reducing power (i.e. lower
Oxidation-reduction potential), meanwhile, it because solubilised state is presented in water body, can further act on, generate with the hydrogen peroxide of generation
Strong homogeneous Fenton effects, so, under the conditions of both complexs can be existing for molecular oxygen, organic contamination of degrading
Object.But since EDTA and four polyphosphoric acids will produce secondary pollution in water body so that existing iron complex reduction generated
The method of hydrogen oxide can not be applied in field of environment protection such as sewage disposals.
Invention content
To overcome the shortcomings of that art methods, the present invention propose a kind of ferrous iron-silicic acid complex activate molecular oxygen, produce
The method of raw hydrogen peroxide.Two silicic acid of silicic acid and stratiform can be formed deliquescent with ferrous ion in the section of pH 5-9
Complex is (with SIL-Fe2+Indicate), which has lower oxidation-reduction potential, the oxygen that can be dissolved in water body
Son direct-reduction, generates hydrogen peroxide.
A kind of ferrous iron-silicic acid complex activate molecular oxygen generates the method for treating water of hydrogen peroxide in situ, as described in Figure 1,
Include the following steps：Soluble silicate is added into organic wastewater, the pH value for adjusting solution is 5-9, be then added it is ferrous from
Son, silicate and ferrous ion form ferrous iron-silicic acid complex (SIL-Fe2+Complex)；It is continually fed into oxygen or air, it is sub-
Iron-silicic acid complex is to O2One-electron reduction is carried out, ultra-oxygen anion free radical O is generated2, ultra-oxygen anion free radical is into one
Step is reduced to H2O2, to make to generate homogeneous Fenton oxidation effect in organic wastewater in situ.
The soluble silicate is sodium metasilicate or sodium disilicate.
The ferrous ion adds in the following manner：(i) it is directly added into divalent iron salt；(ii) it is electrolysed and is produced by iron anode
Raw or (iii) is generated by zeroth order iron rot.
The divalent iron salt includes ferrous sulfate, frerrous chloride, iron ammonium sulfate etc..
The Zero-valent Iron is micron Zero-valent Iron or nano zero valence iron.
When the ferrous ion is electrolysed generation by iron anode, entire water treatment procedure continues galvanization, and anode is using casting
Iron electrode.
A concentration of 2-50mmol/L of soluble silicate in system.
A concentration of 1-10mmol/L of system ferrous ions.
The principles of chemistry of the present invention are as follows：
[SIL-Fe2+]+O2→[SIL-Fe3+]+·O2 -
[SIL-Fe2+]+·O2 -+2H2O→[SIL-Fe3+]+H2O2+2OH-
[SIL-Fe2+]+H2O2→[SIL-Fe3+]+·OH+OH-
Fig. 2 gives SIL-Fe2+With Fe in acid solution3+/Fe2+The comparison of electricity pair, it was demonstrated that the oxidation of this complex is also
Really low than the oxidation-reduction potential of ferrous ion/iron ion of the pH=3 nearly 1.1V vs.SCE. of former current potential are due to SIL-
Fe2+One-electron reduction occurs for the presence of complex, the dissolved oxygen in water, and the hydrogen peroxide of generation is finally anti-with ferrous coordination compound
It answers, generates a large amount of hydroxyl radical free radical, efficient degradation mineralising can be carried out to pollutant.Compared to more existing ferrous coordination compound
System is compared, and silicate is as a kind of nontoxic, harmless inorganic builder agent, and first, itself will not decompose, will not with wait for
The carbon containing organic pollution of degradation competes hydroxyl radical free radical, and the existing various sewage discharge marks of country are complied fully with for water process
Accurate (silicone content is not draining water quality detection index).
Can include sodium metasilicate, sodium disilicate with the ferrous silicate for forming complex in the present invention, silicic acid in system
A concentration of 2-50mmol/L of salt.Simultaneously, it is desirable that the pH of solution ranging from 5~9, outside this section, pH is too low, then it is ferrous from
Son mainly exists with free non-fit form, and pH is excessively high, and ferrous ion is combined with hydroxyl, forms iron hydroxide, can not
Form good SIL-Fe2+Complex.
In the case that initial ferrous ion concentration is 1-10mmol/L, the hydrogen peroxide that can generate in aqueous solution it is flat
Weigh a concentration of 0.1mM-2mM.The hydrogen peroxide of generation can generate homogeneous Fenton effects by following reaction：
[SIL-Fe2+]+H2O2→[SIL-Fe3+]+·OH+OH-
Fenton reactions can further organic substances such as oxidation dye, pesticide, antibiotic, realize the target of wastewater treatment.
In this method, ferrous ion can derive from natural water, can be generated by the divalent iron salt being manually added in solution, can
To be occurred by Zero-valent Iron and reactant aqueous solution, it can also be electrolysed and be generated by iron anode.The present invention is in necks such as environment remediation, water process
Domain has wide practical use.
Description of the drawings
Fig. 1 is the method for treating water schematic diagram that ferrous iron-silicic acid complex activate molecular oxygen generates hydrogen peroxide in situ；
Fig. 2 is the SIL-Fe under different condition2+With Fe in acid solution3+/Fe2+Cyclic voltammogram (the redox of electricity pair
Current potential compares).
Fig. 3 is that whether there is or not H under sodium disilicate existence condition2O2The comparison diagram of concentration changes with time.
Fig. 4 is that whether there is or not the comparison diagrams that chlorophenol residual rate changes over time under ferrous-two silicic acid complex existence conditions.
Fig. 5 is H under different current densities2O2The comparison diagram of concentration changes with time.
Fig. 6 is the comparison diagram that the residual rate of chlorophenol under different current densities changes over time.
Specific implementation mode
Carry out the technical solution that the present invention is further explained below by way of specific embodiment, but protection scope of the present invention is not
It is confined to following embodiment.
Embodiment 1
Using additional ferrous sulfate as ferrous source.The water-soluble of 250mL 20mg/L containing chlorophenol is added in 500mL beakers
Liquid, and the sodium disilicate of 20mmol/L is added uses sulfuric acid to adjust initial pH value as 7.5, the sulfuric acid of 5mmol/L is then added
Ferrous iron, and pass through purity oxygen (rate 2mL/s).Chlorophenol and hydrogen peroxide is dense in specific sample time, measurement system
Degree.Wherein the concentration of chlorophenol is measured by liquid chromatogram measuring, hydrogen peroxide by titanium salt method.As a contrast, another group of experiment, is not added with
Enter sodium disilicate, the pH of solution is only adjusted to 7.5, and 5mmol/L ferrous sulfate is added, and is taken in the identical reaction time
Sample measures chlorophenol concentration and hydrogen peroxide.From figure 3, it can be seen that in having solution existing for sodium disilicate, produce
The hydrogen peroxide of the concentration of hydrogen peroxide peak value of 0.2mmol/L, this concentration is gradually used up with the decomposition of pollutant chlorophenol.
It can be seen from figure 4 that in having solution existing for ferrous-two silicic acid complexs, the concentration of chlorophenol has dropped 40%, illustrates to produce
Raw hydrogen peroxide and ferrous-two silicic acid complexs act on, and produce homogeneous Fenton effects, effectively degrade chlorophenol pollution
Object.
Embodiment 2
Ferrous ion is generated by the way of electrolysis as ferrous source.Using cast iron anode and ruthenium titanium cathode composition electrolysis system
The temperature of system, the built-in 175mL chlorophenols solution of electrolytic cell, the wherein a concentration of 20mg/L of chlorophenol, outer loop water is 25 DEG C, is used
Sodium disilicate is as chelating agent, a concentration of 5mmol/L of sodium disilicate, and system initial pH value is 7.5, electric current be 5mA (or
10mA or 20mA), it is passed through oxygen.The concentration of hydrogen peroxide and chlorophenol in specific time point determining system, test method
With embodiment 2.As a result as shown in Figure 5 and Figure 6, it can be seen that when using sodium disilicate as electrolyte, the peroxidating in solution
Hydrogen cumulative concentration constantly increases, and by cell reaction in three hours, under the conditions of 20mA, the concentration of hydrogen peroxide rose to
0.85mmol/L.Meanwhile chlorophenol has been degraded 95% or more (20mA conditions), illustrates that this method extremely has the degradation of chlorophenol
Effect.
Embodiment 3
Ferrous ion is generated by the way of micron order Zero-valent Iron.250mL 20mg/L containing phenol are added in 500mL beakers
Aqueous solution, and the sodium disilicate of 10mmol/L is added, uses sulfuric acid to adjust initial pH value as 7.5, the micro- of 5g is then added
The Zero-valent Iron of meter level grain size, and by purity oxygen (2mL/s), and agitating solution, so that the zero-valent iron particle in solution is in and suspends
State.In specific sample time, pass through the concentration of phenol in liquid chromatogram measuring system.As a contrast, it is added without for another group
Sodium disilicate, is only added Zero-valent Iron, and other conditions are identical.The result shows that by reaction in 2 hours, containing 10mmol/L's
In the solution of sodium disilicate, the removal rate of phenol has been more than 80%, and in control experiment group, the removal rate of phenol only has 20%.
The result shows in the solution containing sodium disilicate, there are strong destruction of phenol processes, i.e., by hydrogen peroxide original
Position generates induced Fenton oxidation process.
Claims (8)
1. a kind of ferrous iron-silicic acid complex activate molecular oxygen generates the method for treating water of hydrogen peroxide in situ, which is characterized in that packet
Include following steps：Soluble silicate is added into organic wastewater, the pH value for adjusting solution is 5-9, and ferrous ion is then added,
Silicate and ferrous ion form ferrous iron-silicic acid complex；It is continually fed into oxygen or air, ferrous iron-silicic acid complex is to O2Into
Row one-electron reduction generates ultra-oxygen anion free radical O2 -, ultra-oxygen anion free radical is further reduced to H2O2, to
Make to generate homogeneous Fenton oxidation effect in organic wastewater in situ.
2. method for treating water according to claim 1, it is characterised in that：The soluble silicate be sodium metasilicate or
Sodium disilicate.
3. method for treating water according to claim 1, it is characterised in that：The ferrous ion adds in the following manner
Add：(i) it is directly added into divalent iron salt；(ii) generation is electrolysed by iron anode or (iii) is generated by zeroth order iron rot.
4. method for treating water according to claim 3, it is characterised in that：Divalent iron salt include ferrous sulfate, frerrous chloride,
Iron ammonium sulfate etc..
5. method for treating water according to claim 3, it is characterised in that：The ferrous ion is electrolysed by iron anode and is generated
When, entire water treatment procedure continues galvanization, and anode uses cast iron anode.
6. method for treating water according to claim 3, it is characterised in that：The Zero-valent Iron for micron Zero-valent Iron or is received
Rice Zero-valent Iron.
7. method for treating water according to claim 1, it is characterised in that：A concentration of 2- of soluble silicate in system
50mmol/L。
8. method for treating water according to claim 1, it is characterised in that：A concentration of 1- of system ferrous ions
10mmol/L。
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| CN111189823B (en) * | 2020-02-25 | 2022-02-25 | 陕西师范大学 | TMB color development system and application thereof in detection of reducing substances |
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