CN114956299B - Method for regulating and controlling oxidation/reduction degradation pollutant of ferrous/polyphosphate system - Google Patents

Method for regulating and controlling oxidation/reduction degradation pollutant of ferrous/polyphosphate system Download PDF

Info

Publication number
CN114956299B
CN114956299B CN202210780312.3A CN202210780312A CN114956299B CN 114956299 B CN114956299 B CN 114956299B CN 202210780312 A CN202210780312 A CN 202210780312A CN 114956299 B CN114956299 B CN 114956299B
Authority
CN
China
Prior art keywords
pollutants
treated
ferrous
ions
degradation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202210780312.3A
Other languages
Chinese (zh)
Other versions
CN114956299A (en
Inventor
秦传玉
张成武
杨安琪
王瑛琪
白静
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jilin University
Original Assignee
Jilin University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jilin University filed Critical Jilin University
Priority to CN202210780312.3A priority Critical patent/CN114956299B/en
Publication of CN114956299A publication Critical patent/CN114956299A/en
Application granted granted Critical
Publication of CN114956299B publication Critical patent/CN114956299B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • 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
    • C02F1/70—Treatment of water, waste water, or sewage by reduction
    • 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
    • C02F1/727—Treatment of water, waste water, or sewage by oxidation using pure oxygen or oxygen rich gas
    • 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
    • C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)

Abstract

The application provides a method for regulating and controlling oxidation/reduction degradation pollutants of a ferrous/polyphosphate system, which relates to the field of environmental protection and comprises the following steps of 2+ /O 2 TPP system degradation by controlling system pH and TPP/Fe 2+ Molar concentration ratio of (2) to regulate and control the molar concentration ratio of OH and O in the system 2 ·‑ Thereby achieving the purpose of controlling the oxidation/reduction degradation of pollutants in the system. The scheme regulates and controls the OH and O in the system by changing the reaction conditions 2 ·‑ The effect contribution of the system realizes the purpose of controlling the oxidation/reduction degradation of pollutants in the system, effectively solves the problem of poor effect of the system on removing the pollutants difficult to be oxidized and degraded, greatly widens the application range of the system, and has the advantages of simple process, low cost, environmental protection and the like compared with the traditional technology for regulating and controlling the oxidation/reduction degradation of the pollutants.

Description

Method for regulating and controlling oxidation/reduction degradation pollutant of ferrous/polyphosphate system
Technical Field
The application relates to the field of environmental protection, in particular to a method for regulating and controlling oxidation/reduction degradation of pollutants by a ferrous/polyphosphate system.
Background
Oxygen is used as a natural green oxidant in the environment, which is difficult to directly oxidize and degrade organic pollutants under natural conditions, but can form hydroxyl radical (OH) and superoxide radical (O) after being activated 2 ·- ) And the active substances have strong reactivity.
In the currently reported oxygen activation methods, ferrous iron becomes an ideal method for activating oxygen due to the characteristics of low price, wide sources, environmental friendliness and the like. Research shows that Fe 2+ Activating oxygen can produce OH, O 2 ·- However, the content of the active material in the system is extremely low, and organic pollutants cannot be removed effectively, so that an appropriate oxygen-containing ligand needs to be added to strengthen the generation of the active material.
The oxygen-containing ligands that have been reported to date include ethylenediamine tetraAcetic acid, nitrilotriacetic acid, citric acid, oxalic acid, polyphosphates, disilicates, and the like. Among them, polyphosphates (TPP) are widely used because they can effectively promote the production of active substances in a system, do not compete with organic pollutants for active species, and are green and nontoxic as food additives. But at present Fe 2+ /O 2 The TPP system is mainly characterized by emphasizing the oxidation of OH and ignoring O in the system 2 ·- The reduction effect of the system is poor in removing pollutants difficult to oxidize and degrade, and the application range is narrow.
Disclosure of Invention
The application aims to provide a method for regulating and controlling oxidation/reduction degradation pollutants of a ferrous/polyphosphate system, which aims to solve the problem that the system has poor effect of removing pollutants difficult to be oxidized and degraded, and greatly widens the application range of the system.
To achieve the above object, the present application provides a method for modulating the oxidative/reductive degradation of contaminants by a ferrous/polyphosphate system, comprising:
adding ferrous ions and polyphosphate into the pollutant to be treated to form a reaction system, and continuously introducing O into the system 2 The molar ratio of the polyphosphate to the ferrous ions is controlled to be changed between 0.5 and 3, and the pH value of the system is controlled to be changed between 2 and 8 so as to carry out oxidative degradation and reductive degradation on the pollutants to be treated.
Preferably, the molar ratio of the polyphosphate to the ferrous ions is controlled to be 1.5-2.5, and the pH of the system is controlled to be changed between 2-8 so as to carry out oxidative degradation and reductive degradation on the pollutants to be treated;
when the pH value of the system is controlled to be 2-4, the pollutants to be treated are subjected to oxidative degradation mainly;
and when the pH value of the system is controlled to be 4-8, reducing and degrading the pollutants to be treated.
Preferably, the molar ratio of the polyphosphate to the ferrous ions is controlled to be 2, and the pH of the system is controlled to be changed between 3 and 7 so as to carry out oxidative degradation and reductive degradation on the pollutants to be treated;
when the pH value of the system is controlled to be 3-4, the pollutants to be treated are subjected to oxidative degradation mainly;
and when the pH value of the system is controlled to be 5-7, reducing and degrading the pollutants to be treated.
Preferably, the pH of the system is controlled to be 6-8, and the molar ratio of the polyphosphate to the ferrous ions is controlled to be 0.5-3 so as to carry out oxidative degradation and reductive degradation on the pollutants to be treated;
wherein, when the mole ratio of the polyphosphate to the ferrous ions is controlled to be 0.5-1, the pollutants to be treated are mainly subjected to oxidative degradation;
and when the molar ratio of the polyphosphate to the ferrous ions is controlled to be more than 1 and less than or equal to 3, reducing and degrading the pollutants to be treated.
Preferably, the pH of the system is controlled to 7, and the molar ratio of the polyphosphate to the ferrous ions is controlled to be varied between 0.5 and 3 so as to carry out oxidative degradation and reductive degradation on the pollutants to be treated;
wherein, when the mole ratio of the polyphosphate to the ferrous ions is controlled to be 0.5-1, the pollutants to be treated are mainly subjected to oxidative degradation;
and when the molar ratio of the polyphosphate to the ferrous ions is controlled to be 2-3, reducing and degrading the pollutants to be treated.
Preferably, the ferrous ion is selected from any one or more of ferrous sulfate, ferrous chloride and ferrous hydroxide.
Preferably, the polyphosphate ions comprise tetraphosphoric acid ions and/or tripolyphosphoric acid ions.
Preferably, the tetraphosphoric acid ions comprise any one or more of tetraphosphoric acid, sodium tetraphosphoric acid, potassium tetraphosphoric acid, and ammonium tetraphosphoric acid; the tripolyphosphate ions include any one or more of tripolyphosphate, sodium tripolyphosphate, potassium tripolyphosphate, and ammonium tripolyphosphate.
Preferably, the O 2 The flow rate of the catalyst is 100-200 mL/min.
Compared with the prior art, the beneficial effects of this application include:
the method for degrading the pollutants provided by the application is Fe 2+ /O 2 TPP system degradation by controlling system pH and TPP/Fe 2+ Molar concentration ratio of (2) to regulate and control the molar concentration ratio of OH and O in the system 2 ·- Thereby achieving the purpose of controlling the oxidation/reduction degradation of pollutants in the system. The scheme regulates and controls the OH and O in the system by changing the reaction conditions 2 ·- The effect contribution of the system realizes the purpose of controlling the oxidation/reduction degradation of pollutants in the system, effectively solves the problem of poor effect of the system on removing the pollutants difficult to be oxidized and degraded, greatly widens the application range of the system, and has the advantages of simple process, low cost, environmental protection and the like compared with the traditional technology for regulating and controlling the oxidation/reduction degradation of the pollutants.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate certain embodiments of the present application and therefore should not be considered as limiting the scope of the present application.
FIG. 1 is a graph of Fe at different pH conditions 2+ /O 2 A graph of the results of the TPP system degradation of contaminants;
FIG. 2 shows different TPP/Fe 2+ Fe at a molar ratio of 2+ /O 2/ Results of TPP system degradation of contaminants.
Detailed Description
The term as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprising," "including," "having," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified element, step or component. If used in a claim, such phrase will cause the claim to be closed, such that it does not include materials other than those described, except for conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the claim body, rather than immediately following the subject, it is limited to only the elements described in that clause; other elements are not excluded from the stated claims as a whole.
When an equivalent, concentration, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"parts by mass" means a basic unit of measurement showing the mass ratio of a plurality of components, and 1 part may be any unit mass, for example, 1g may be expressed, 2.689g may be expressed, and the like. If we say that the mass part of the a component is a part and the mass part of the B component is B part, the ratio a of the mass of the a component to the mass of the B component is represented as: b. alternatively, the mass of the A component is aK, and the mass of the B component is bK (K is an arbitrary number and represents a multiple factor). It is not misunderstood that the sum of the parts by mass of all the components is not limited to 100 parts, unlike the parts by mass.
"and/or" is used to indicate that one or both of the illustrated cases may occur, e.g., a and/or B include (a and B) and (a or B).
The present application provides a method of modulating the oxidative/reductive degradation of contaminants of a ferrous/polyphosphate system, such as may be used to treat waste solutions, or the solution state of solid contaminants, comprising: adding ferrous ions and polyphosphate into the pollutant to be treated to form a reaction system, and continuously introducing O into the system 2 The molar ratio of the polyphosphate to the ferrous ions is controlled to be changed between 0.5 and 3, and the pH value of the system is controlled to be changed between 2 and 8 so as to carry out oxidative degradation and reductive degradation on the pollutants to be treated.
The method for degrading the pollutants provided by the application is Fe 2+ /O 2 TPP system degradation by controlling system pH and TPP/Fe 2+ Molar concentration ratio of (2) to regulate and control the molar concentration ratio of OH and O in the system 2 ·- Thereby achieving the purpose of controlling the oxidation/reduction degradation of pollutants in the system. The scheme regulates and controls the OH and O in the system by changing the reaction conditions 2 ·- The effect contribution of the system realizes the purpose of controlling the oxidation/reduction degradation of pollutants in the system, effectively solves the problem of poor effect of the system on removing the pollutants difficult to be oxidized and degraded, greatly widens the application range of the system, and has the advantages of simple process, low cost, environmental protection and the like compared with the traditional technology for regulating and controlling the oxidation/reduction degradation of the pollutants.
Wherein, the ferrous ion is the ferrous ion in a dissolved state, and the scheme is not applicable to solid minerals containing Fe (II). The ferrous ions may be selected from any one or more of ferrous sulfate, ferrous chloride, ferrous hydroxide, for example.
Wherein the polyphosphate ion comprises a tetraphosphoric acid ion and/or a tripolyphosphoric acid ion. The tetraphosphoric acid radical ion comprises any one or more of tetraphosphoric acid, sodium tetraphosphoric acid, potassium tetraphosphoric acid and ammonium tetraphosphoric acid; the tripolyphosphate ions include any one or more of tripolyphosphate, sodium tripolyphosphate, potassium tripolyphosphate, and ammonium tripolyphosphate.
Wherein O is 2 The air can be introduced into the system in the form of air or pure oxygen, and the air is introduced into the system in the form of pure oxygenThis is not particularly limited. The O is 2 The flow rate of (C) may be, for example, 100 to 200mL/min, for example, 100mL/min, 120mL/min, 150mL/min, 160mL/min, 180mL/min or 200mL/min.
The reaction mechanism of the system comprises the following processes:
O 2 +Fe(TPP) 2+ →O 2 ·- +Fe(TPP) 3+
O 2 ·- +Fe(TPP) 2+ +2H + →H 2 O 2 +Fe(TPP) 3+
Fe(TPP) 2+ +H 2 O 2 →Fe(TPP) 3+ +2·OH
on the one hand, the generation process of the reaction mechanism is strongly influenced by the pH of the solution, and when the pH is low, for example, 2-4, O in the system 2 O produced by activation 2 ·- The organic acid is quickly converted into OH, the system has strong oxidizing property, and pollutants are oxidized and degraded; when the pH is relatively high, for example, 4 to 8, O in the system 2 ·- To H 2 O 2 The conversion rate is obviously inhibited, resulting in O in solution 2 ·- The system has strong reducibility, so that the pollutants are reduced and degraded. Thus, the pH adjustment can be used to adjust whether the system is suitable for oxidative degradation or reductive degradation. In a pollutant to be treated, there are generally substances which require oxidative degradation and reductive degradation, and the pH is adjusted to be in the range of 2 to 8 in a reaction system to degrade different substances.
On the other hand, TPP/Fe in solution 2+ The molar ratio changes Fe in the system 2+ -composition of TPP complex. Fe in the system under neutral condition 2+ The TPP complex is mainly composed of [ Fe (H) 2 O) 6 ] 2+ 、[Fe(TPP)(H 2 O) 3 ] - And [ Fe (TPP) 2 ] 4- In which [ Fe (TPP) (H) 2 O) 3 ] - And [ Fe (TPP) 2 ] 4- For O in the system 2 ·- The production has obvious activity, and the production of OH is mainly carried out by [ Fe (TPP) (H 2 O) 3 ] - Mainly.
When Fe in the system 2+ When the concentration is higher than the TPP concentration, the complex in the system mainly adopts [ Fe (TPP) (H) 2 O) 3 ] - Mainly, O 2 ·- Is rapidly activated to generate OH, the system has strong oxidizing property, and the pollutants are oxidized and degraded; when Fe in the system 2+ When the concentration is smaller than the TPP concentration, the system is mainly composed of [ Fe (TPP) 2 ] 4- Mainly, at this time O 2 Is activated to produce a large amount of O 2 ·- The system has strong reducibility, and the pollutants are reduced and degraded. Therefore, the scheme can also regulate and control TPP/Fe in the system 2+ The molar ratio is varied to effect the oxidative/reductive degradation of the contaminants.
It can be understood that the system has good reduction and degradation for organic pollutants containing electron withdrawing groups such as halogen or nitro; the system can be well oxidized and degraded for pollutants containing electron donating groups such as hydroxyl or methyl.
In one embodiment, the molar ratio of the polyphosphate ion to the ferrous ion is controlled to be 1.5-2.5, for example, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4 or 2.5; controlling the pH of the system to change between 2 and 8 so as to carry out oxidative degradation and reductive degradation on the pollutants to be treated.
Wherein, when the pH of the system is controlled to be 2-4, O in the system 2 O produced by activation 2 ·- Rapidly converts into OH, has strong oxidability, and mainly performs oxidative degradation on the pollutants to be treated.
Wherein, when the pH of the system is controlled to be 4-8, O in the system 2 ·- To H 2 O 2 The conversion rate is obviously inhibited, resulting in O in solution 2 ·- The system has strong reducibility, and the pollutants to be treated are mainly reduced and degraded.
In a preferred embodiment, the pH of the system is controlled to be 3-4 to effect oxidative degradation of the contaminants to be treated.
In a preferred embodiment, the molar ratio of the polyphosphate ions to the ferrous ions is controlled to be 2, and the pH of the system is controlled to be changed between 3 and 7 so as to carry out oxidative degradation and reductive degradation on the pollutants to be treated.
Wherein, when the pH value of the system is controlled to be 3-4, the pollutant to be treated is mainly subjected to oxidative degradation. Controlling the pH value of the system to be 5-7, and mainly reducing and degrading the pollutants to be treated.
In another embodiment, the pH of the system is controlled to be 6-8, for example, the pH may be 6, 7 or 8, and the molar ratio of the polyphosphate ions to the ferrous ions is controlled to vary between 0.5 and 3 to effect oxidative and reductive degradation of the contaminants to be treated.
Wherein when the molar ratio of the polyphosphate radical ion to the ferrous ion is controlled to be 0.5-1, the complex in the system mainly comprises [ Fe (TPP) (H) 2 O) 3 ] - Mainly, O 2 ·- Is rapidly activated to produce OH, the system has strong oxidizing property, and the pollutants to be treated are mainly subjected to oxidative degradation.
Wherein when the molar ratio of the polyphosphate ions to the ferrous ions is controlled to be more than 1 and less than or equal to 3, the system is mainly composed of [ Fe (TPP) 2 ] 4- Mainly, at this time O 2 Is activated to produce a large amount of O 2 ·- The system has strong reducibility and mainly reduces and degrades the pollutants to be treated.
Preferably, the pH of the system is controlled to be 7, and the molar ratio of the polyphosphate ions to the ferrous ions is controlled to be between 0.5 and 3 so as to carry out oxidative degradation and reductive degradation on the pollutants to be treated;
wherein, when the mole ratio of the polyphosphate radical ion to the ferrous ion is controlled to be 0.5-1, the pollutant to be treated is mainly subjected to oxidative degradation;
and when the molar ratio of the polyphosphate ions to the ferrous ions is controlled to be 2-3, reducing and degrading the pollutants to be treated.
Embodiments of the present application will be described in detail below with reference to specific examples, but it will be understood by those skilled in the art that the following examples are only for illustration of the present application and should not be construed as limiting the scope of the present application. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention. The volume of the system solution in the examples was 100ml without any particular explanation.
Example 1
Adding 20mM TPP (sodium tripolyphosphate) and 10mM Fe into 10mg/L p-nitrophenol solution to be treated 2+ (FeSO 4 ·7H 2 O) by stirring or shaking TPP and Fe 2+ Dissolving, continuously providing air into the system, adjusting the pH value of the system to 3 at the air flow rate of 150ml/min, and detecting the degradation condition of the p-nitrophenol.
Adding 20mM TPP and 10mM Fe into 10mg/L benzoic acid solution to be treated 2+ By stirring or shaking TPP and Fe 2+ Dissolving, continuously providing air into the system, adjusting the pH value of the system to 3 at the air flow rate of 150ml/min, and detecting the degradation condition of the benzoic acid.
Example 2
Adding 20mM TPP and 10mM Fe into 10mg/L p-nitrophenol solution to be treated 2+ By stirring or shaking TPP and Fe 2+ Dissolving, continuously providing air into the system, adjusting the pH value of the system to 5 at the air flow rate of 150ml/min, and detecting the degradation condition of the p-nitrophenol.
Adding 20mM TPP and 10mM Fe into 10mg/L benzoic acid solution to be treated 2+ By stirring or shaking TPP and Fe 2+ Dissolving, continuously providing air into the system, adjusting the pH value of the system to 5 at the air flow rate of 150ml/min, and detecting the degradation condition of the benzoic acid.
Example 3
Adding 20mM TPP and 10mM Fe into 10mg/L p-nitrophenol solution to be treated 2+ By stirring or shaking TPP and Fe 2+ Dissolution followed by continuous supply of air to the system at an air flow rate of 150ml/min, regulating the pH value of the system to 7, and detecting the degradation condition of the p-nitrophenol.
Adding 20mM TPP and 10mM Fe into 10mg/L benzoic acid solution to be treated 2+ By stirring or shaking TPP and Fe 2+ Dissolving, continuously providing air into the system, adjusting the pH value of the system to 7 at the air flow rate of 150ml/min, and detecting the degradation condition of the benzoic acid.
Fe under different pH conditions of examples 1 to 3 2+ /O 2 The results of the degradation of contaminants by the TPP system are shown in FIG. 1. When the pH of the solution is=3, OH plays a main role in the system, and pollutants are mainly oxidized and degraded; when the pH of the solution is=5 or 7, O in the system 2 ·- Plays a main role, and the paranitrophenol is mainly reduced and degraded for substances which are difficult to oxidize and easily reduce.
FIG. 1 shows the removal effect of the system on para-nitrophenol (a difficult to oxidize and easily reducible material) and benzoic acid (a difficult to oxidize and easily reducible material) at different pH conditions. It can be seen that the system has the best effect on degradation of the difficult-to-oxidize and easy-to-reduce p-nitrophenol at the pH value of=5, and the reduction degradation of the p-nitrophenol is obviously stronger than that of the p-nitrophenol at the pH values of=5 and 7; for benzoic acid which is easy to oxidize and difficult to reduce, the degradation effect of the system is best under the condition of pH=3, and the oxidative degradation of the benzoic acid is obviously stronger than the reductive degradation.
Example 4
5mM TPP and 10mM Fe are added to 5mg/L tetrabromobisphenol A solution to be treated 2+ By stirring or shaking TPP and Fe 2+ Dissolving, continuously providing air to the system, adjusting the pH value of the system to be 7 at the air flow rate of 150ml/min, and detecting the degradation condition of tetrabromobisphenol A.
Adding 5mM TPP and 10mM Fe into 10mg/L phenol solution to be treated 2+ By stirring or shaking TPP and Fe 2+ Dissolving, continuously providing air to the system, adjusting the pH value of the system to 7 at the air flow rate of 150ml/min, and detecting the degradation condition of phenol.
Example 5
To 5mg/L tetrabromobisphenol A solution to be treated, 10mM TPP and 10mM Fe were added 2+ By stirring or shaking TPP and Fe 2+ Dissolving, continuously providing air to the system, adjusting the pH value of the system to be 7 at the air flow rate of 150ml/min, and detecting the degradation condition of tetrabromobisphenol A.
10mM TPP and 10mM Fe are added to a 10mg/L phenol solution to be treated 2+ By stirring or shaking TPP and Fe 2+ Dissolving, continuously providing air to the system, adjusting the pH value of the system to 7 at the air flow rate of 150ml/min, and detecting the degradation condition of phenol.
Example 6
To 5mg/L tetrabromobisphenol A solution to be treated, 20mM TPP and 10mM Fe were added 2+ By stirring or shaking TPP and Fe 2+ Dissolving, continuously providing air to the system, adjusting the pH value of the system to be 7 at the air flow rate of 150ml/min, and detecting the degradation condition of tetrabromobisphenol A.
Adding 20mM TPP and 10mM Fe into 10mg/L phenol solution to be treated 2+ By stirring or shaking TPP and Fe 2+ Dissolving, continuously providing air to the system, adjusting the pH value of the system to 7 at the air flow rate of 150ml/min, and detecting the degradation condition of phenol.
Example 7
To 5mg/L tetrabromobisphenol A solution to be treated, 30mM TPP and 10mM Fe were added 2+ By stirring or shaking TPP and Fe 2+ Dissolving, continuously providing air to the system, adjusting the pH value of the system to be 7 at the air flow rate of 150ml/min, and detecting the degradation condition of tetrabromobisphenol A.
Adding 30mM TPP and 10mM Fe into 10mg/L phenol solution to be treated 2+ By stirring or shaking TPP and Fe 2+ Dissolving, continuously providing air to the system, adjusting the pH value of the system to 7 at the air flow rate of 150ml/min, and detecting the degradation condition of phenol.
Examples 4 to 7 different TPP/Fe 2+ Fe at a molar ratio of 2+ /O 2 The results of the degradation of contaminants by the/TPP system are shown in FIG. 2. FIG. 2 shows the system at different TPP/Fe 2+ Tetrabromobisphenol A at molar ratioSubstances difficult to oxidize and easily reduced) and phenol (substances difficult to oxidize and easily reduced). As can be seen, the system is used for tetrabromobisphenol A in TPP/Fe 2+ Molar ratio of>The degradation effect in 1 is obviously better than that of TPP/Fe 2+ Molar ratio of less than or equal to 1, and TPP/Fe 2+ Molar ratio of>The tetrabromobisphenol A has the best reduction degradation effect in the step 1; for phenol, the system is TPP/Fe 2+ The degradation effect is best under the condition that the molar ratio is less than or equal to 1, and the oxidative degradation of phenol is obviously stronger than the reductive degradation.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions from the scope of the technical solutions of the embodiments of the present application.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features but not others included in other embodiments, combinations of features of different embodiments are meant to be within the scope of the present application and form different embodiments. For example, in the claims below, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the application and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.

Claims (7)

1. A method of modulating the oxidative/reductive degradation of a contaminant of a ferrous/polyphosphate system comprising:
adding ferrous ions and polyphosphate ions into pollutants to be treated to form a reaction system, and continuously introducing O into the system 2 ；
Controlling the mole ratio of the polyphosphate radical ion to the ferrous ion to be 1.5-2.5, and controlling the pH value of the system to be changed between 2-8 so as to carry out oxidative degradation and reductive degradation on the pollutants to be treated;
when the pH value of the system is controlled to be 2-4, the pollutants to be treated are subjected to oxidative degradation mainly;
when the pH value of the system is controlled to be 4-8, the pollutant to be treated is mainly reduced and degraded;
or controlling the pH of the system to be 6-8, and controlling the molar ratio of the polyphosphate ions to the ferrous ions to be 0.5-3 so as to carry out oxidative degradation and reductive degradation on the pollutants to be treated;
wherein, when the mole ratio of the polyphosphate radical ion to the ferrous ion is controlled to be 0.5-1, the pollutant to be treated is mainly subjected to oxidative degradation;
and when the molar ratio of the polyphosphate ions to the ferrous ions is controlled to be more than 1 and less than or equal to 3, reducing and degrading the pollutants to be treated.
2. The method according to claim 1, characterized in that the molar ratio of the polyphosphate ions to the ferrous ions is controlled to be 2, the pH of the system is controlled to vary between 3 and 7, so as to carry out oxidative degradation and reductive degradation of the contaminants to be treated;
when the pH value of the system is controlled to be 3-4, the pollutants to be treated are subjected to oxidative degradation mainly;
and when the pH value of the system is controlled to be 5-7, reducing and degrading the pollutants to be treated.
3. The method according to claim 1, characterized in that the pH of the system is controlled to 7, the molar ratio of the polyphosphate ions to the ferrous ions is controlled to vary between 0.5 and 3, in order to carry out oxidative and reductive degradation of the contaminants to be treated;
wherein, when the mole ratio of the polyphosphate radical ion to the ferrous ion is controlled to be 0.5-1, the pollutant to be treated is mainly subjected to oxidative degradation;
and when the molar ratio of the polyphosphate ions to the ferrous ions is controlled to be 2-3, reducing and degrading the pollutants to be treated.
4. A method according to any one of claims 1 to 3, wherein the ferrous ions are selected from any one or more of ferrous sulphate, ferrous chloride, ferrous hydroxide.
5. A method according to any one of claims 1 to 3, wherein the polyphosphate ions comprise tetraphosphoric acid ions and/or tripolyphosphoric acid ions.
6. The method of claim 5, wherein the tetraphosphoric acid ions comprise any one or more of tetraphosphoric acid, sodium tetraphosphoric acid, potassium tetraphosphoric acid, and ammonium tetraphosphoric acid; the tripolyphosphate ions include any one or more of tripolyphosphate, sodium tripolyphosphate, potassium tripolyphosphate, and ammonium tripolyphosphate.
7. The method of claim 1, wherein the O 2 The flow rate of the catalyst is 100-200 mL/min.
CN202210780312.3A 2022-07-04 2022-07-04 Method for regulating and controlling oxidation/reduction degradation pollutant of ferrous/polyphosphate system Active CN114956299B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210780312.3A CN114956299B (en) 2022-07-04 2022-07-04 Method for regulating and controlling oxidation/reduction degradation pollutant of ferrous/polyphosphate system

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210780312.3A CN114956299B (en) 2022-07-04 2022-07-04 Method for regulating and controlling oxidation/reduction degradation pollutant of ferrous/polyphosphate system

Publications (2)

Publication Number Publication Date
CN114956299A CN114956299A (en) 2022-08-30
CN114956299B true CN114956299B (en) 2023-07-14

Family

ID=82968247

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210780312.3A Active CN114956299B (en) 2022-07-04 2022-07-04 Method for regulating and controlling oxidation/reduction degradation pollutant of ferrous/polyphosphate system

Country Status (1)

Country Link
CN (1) CN114956299B (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2376725A1 (en) * 2001-03-21 2002-09-21 Air Products And Chemicals, Inc. Treatment of water containing organic wastes with aromatic amine nitrate salts
KR20160102926A (en) * 2016-06-17 2016-08-31 주식회사 오이코스 Reductive-oxidative treatment method and apparatus of water pollutants by zero-valent iron/polyphosphates at neutral pH
CN113087208A (en) * 2021-02-03 2021-07-09 南京水滴智能环保装备研究院有限公司 Method for degrading copper ore wastewater by using synergistic catalytic oxidation system

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8834725B2 (en) * 2011-01-31 2014-09-16 Chevron U.S.A. Inc. Method for treating acid mine drainage
CN103240267B (en) * 2013-04-28 2014-07-23 华中师范大学 Soil restoration method based on oxygen activation of iron powder and polyphosphoric acid molecules
CN103864183B (en) * 2014-03-21 2016-02-10 华中师范大学 A kind of neutrality electricity Fenton oxidation water treatment method of coupled molecule oxygen activation
US10118061B2 (en) * 2014-10-17 2018-11-06 Trojan Technologies Catalyst and process for treatment of fluid comprising an oxidizable contaminant
FR3054543B1 (en) * 2016-07-28 2018-08-10 Snf Sas PROCESS FOR TREATING PRODUCTION WATER FROM A PROCESS FOR ASSISTED OIL AND / OR GAS RECOVERY
CN106829873B (en) * 2017-03-03 2018-10-26 武汉大学 The method that ferrous iron-silicic acid complex activate molecular oxygen generates hydrogen peroxide in situ
CN109574195A (en) * 2019-01-24 2019-04-05 吉林大学 The method that elemental copper and polyphosphate activation oxygen remove hardly degraded organic substance in water removal
CN110563096B (en) * 2019-09-30 2020-07-10 华中科技大学 Method and device for strengthening electro-Fenton water treatment
US20220355283A1 (en) * 2019-10-01 2022-11-10 Acenet Inc. Drug, drug manufacturing method, and water purification method
CN113023839A (en) * 2021-04-28 2021-06-25 辽宁科技学院 Micro-electrolysis Fenton oxidation water treatment method activated by polyphosphate

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2376725A1 (en) * 2001-03-21 2002-09-21 Air Products And Chemicals, Inc. Treatment of water containing organic wastes with aromatic amine nitrate salts
KR20160102926A (en) * 2016-06-17 2016-08-31 주식회사 오이코스 Reductive-oxidative treatment method and apparatus of water pollutants by zero-valent iron/polyphosphates at neutral pH
CN113087208A (en) * 2021-02-03 2021-07-09 南京水滴智能环保装备研究院有限公司 Method for degrading copper ore wastewater by using synergistic catalytic oxidation system

Also Published As

Publication number Publication date
CN114956299A (en) 2022-08-30

Similar Documents

Publication Publication Date Title
Cheng et al. Removal of phenol by acid-washed zero-valent aluminium in the presence of H2O2
Ma et al. Preliminary investigation of manganese-catalyzed ozonation for the destruction of atrazine
Utset et al. Replacement of H2O2 by O2 in Fenton and photo-Fenton reactions
Pereira et al. Azo dye degradation by recycled waste zero-valent iron powder
Sjogren et al. Inactivation of phage MS2 by iron-aided titanium dioxide photocatalysis
Zelmanov et al. Phenol oxidation kinetics in water solution using iron (3)-oxide-based nano-catalysts
Kimura et al. Discovery of the activated-carbon radical AC+ and the novel oxidation-reactions comprising the AC/AC+ cycle as a catalyst in an aqueous solution.
CA2338943A1 (en) Process for removal and stabilization of arsenic and selenium from aqueous streams and slurries
WO2018184391A1 (en) Method for synchronously removing complex heavy metal and organic substance by magnetic separation
TW201119949A (en) Composition as absorbent and catalyzer, processing method thereof, and method for treating waste water thereof
Yang et al. Degradation of orange II by Fe@ Fe2O3 core shell nanomaterials assisted by NaHSO3
Frim et al. Sonochemical destruction of free and metal-binding ethylenediaminetetraacetic acid
Peng et al. Insights into the enhanced removal of sulfamethoxazole via peroxymonosulfate activation catalyzed by bimetallic (Co/Cu) doped graphitic carbon nitride: reaction kinetics, mechanisms, and pathways
CN103663666A (en) Method for carrying out cooperative oxidation treatment on organic wastewater by potassium permanganate and potassium hydrogen persulfate
CN110560168B (en) Core-shell hierarchical iron/copper bimetallic Fenton catalyst and preparation method and application thereof
Li et al. Low dose of sulfur-modified zero-valent iron for decontamination of trace Cd (II)-complexes in high-salinity wastewater
Song et al. Ligand effects on arsenite removal by zero-valent iron/O2: Dissolution, corrosion, oxidation and coprecipitation
CN114956299B (en) Method for regulating and controlling oxidation/reduction degradation pollutant of ferrous/polyphosphate system
Nguyen et al. Reutilization of Fe-containing tailings ore enriched by iron (iii) chloride as a heterogeneous Fenton catalyst for decolorization of organic dyes
Christoforidis et al. Effect of humic acid on chemical oxidation of organic pollutants by iron (II) and H2O2: a dual mechanism
CN110885145B (en) Method for synchronously removing pollutants in water body and controlling generation of bromine-containing byproducts
CN109437386B (en) Method for removing metal thallium in wastewater
Choi et al. Degradation of acetone and isopropylalcohol in electronic wastewater using Fe-and Al-immobilized catalysts
Ma et al. Dithionite accelerated copper slag heterogeneous-homogeneous coupled Fenton degradation of organic pollutants
CN113600205B (en) Copper-based Cu-Al 2 O 3 Catalyst and application thereof in treatment of estrogen-containing wastewater

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant