CN112142232A - Wastewater directional reconstruction-reinforced separation coupling method - Google Patents

Wastewater directional reconstruction-reinforced separation coupling method Download PDF

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CN112142232A
CN112142232A CN202011119853.9A CN202011119853A CN112142232A CN 112142232 A CN112142232 A CN 112142232A CN 202011119853 A CN202011119853 A CN 202011119853A CN 112142232 A CN112142232 A CN 112142232A
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wastewater
stirring
oxidation
pollutants
combination
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赵赫
曹宏斌
钟晨
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Institute of Process Engineering of CAS
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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
    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular compounds
    • 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
    • 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
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • 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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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)

Abstract

The invention provides a wastewater directional reconstruction-reinforced separation coupling method, which regulates and controls the structure of pollutants through directional reconstruction and reinforces and promotes the oxidative degradation of organic pollutants in water, thereby achieving the high-efficiency detoxification of the organic pollutants.

Description

Wastewater directional reconstruction-reinforced separation coupling method
Technical Field
The invention belongs to the technical field of water treatment, relates to a method for removing pollutants in wastewater, and particularly relates to a method for directional reconstruction-reinforced separation coupling of wastewater.
Background
With the expansion of the production activity range of human beings, the yield and the demand of artificially synthesized organic matters are continuously increased, and a large amount of exogenous organic pollutants enter the water environment, wherein the exogenous organic pollutants comprise but are not limited to emerging pollutants (ECs), byproducts generated in the production process, organic matter intermediates and the like. The concentration of the pollutants in water is relatively low, but the pollutants have high toxicity, can generate abnormal influence on a biological physiological system through various ways such as ingestion, accumulation, excitation variation and the like, have potential cancerogenic and teratogenic effects on a human body, and can cause metabolic disorder or drug resistance of the human body after being exposed to a polluted environment for a long time. The abnormality of the biological physiological system can be gradually enlarged along with the accumulation of biological chains, thereby bringing a great deal of harm to the ecological system and the human health.
The oxidation method is a more common method for detoxifying organic pollutants in water, and CN 104609597A discloses a method for ultra-fast removing organic pollutants in water, wherein hydrogen sulfite is used as a reducing agent to generate active manganese (Mn (III)), so that the efficiency of removing organic pollutants by manganese dioxide and potassium permanganate is improved, but the method has strict requirements on pH value.
CN 102951716A discloses a method for reducing COD in phenolic wastewater by using calcium permanganate, wherein the method adopts calcium permanganate and manganese dioxide generated in situ as oxidants, and reduces COD in phenolic wastewater, but the method has no selectivity to phenolic organic pollutants, and a large amount of oxidants are used for treating easily degradable organic solvents in wastewater, thereby causing resource waste.
CN 205907101U reports a system for treating wastewater with fenton's reagent, which uses fenton's reagent as an oxidant to treat organic pollutants, but the system is not selective for more toxic organic pollutants (such as phenolic organic pollutants) and has a severe requirement on pH.
The coupling process initiated by weak oxidation can significantly change the molecular structure and electronic properties of the organic contaminants, thereby changing the polymerization properties of the organic contaminants. The cross coupling reaction between different organic matters can further improve the polymerization capacity of the organic matters, thereby obtaining organic products with higher molecular weight. Therefore, the method combining polymerization coupling and oxidative degradation has good selectivity on quinones or organic pollutants which are easily oxidized into quinones, and can enhance the removal efficiency and detoxification efficiency of the organic pollutants at low cost.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a wastewater directional reconstruction-reinforced separation coupling method, which can change the structure and electronic characteristics of organic pollutants through directional reconstruction, so that the molecular weight and polymerization degree of the pollutants in the wastewater are changed, the solubility of the pollutants in the wastewater in water is changed, and the separation of the pollutants in the wastewater is promoted; and then, the separation of pollutants in the wastewater is realized in a solid-liquid separation mode.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a wastewater directional reconstruction-reinforced separation coupling method, which comprises the following steps:
(1) directional reconstruction: adding a coupling template agent into the wastewater under an oxidation condition to directionally reconstruct pollutant molecules in the wastewater to a molecular weight of more than 3000 Da;
(2) strengthening and separating: and (3) adding a flocculating agent, and performing flocculation precipitation on the wastewater obtained in the step (1) to realize solid-liquid separation.
The invention carries out directional reconstruction on pollutant molecules in water to lead the pollutants in the water to be cross-coupled, and the pollutants containing amino and/or thiol groups are covalently combined into macromolecular organic matters, thereby obviously changing the electronic distribution of the pollutants, leading the molecular weight of the pollutants to change, promoting the pollutants to be separated out from the wastewater, and finally realizing the removal of the pollutants in the water through solid-liquid separation.
The method disclosed by the invention has the advantages that the separation of the pollutants in the wastewater can be realized only by increasing the molecular weight of the pollutants to more than 3000 Da; as a preferable technical proposal, the molecular weight of the pollutants is increased to more than 3000Da, and the polymerization degree of the pollutants is made to be more than 20, thereby realizing excellent separation effect of the pollutants in the wastewater.
Preferably, the molecular weight of the contaminants in the wastewater of step (1) does not exceed 200Da, and may be, for example, 90Da, 100Da, 110Da, 120Da, 130Da, 140Da, 150Da, 160Da, 170Da, 180Da, 190Da or 200Da, but is not limited to the recited values, and other values not recited in the range are equally applicable.
The molecular weight of the single pollutant is determined by electrospray-mass spectrometry quadrupole time-of-flight mass spectrometry (LC-ESI-QToF).
Preferably, the contaminant comprises any one or combination of at least two of quinone, chloranil, phenol, p-aminophenol or acetaminophen, typical but non-limiting combinations include a combination of quinone and chloranil, a combination of chloranil and phenol, a combination of phenol and p-aminophenol, a combination of p-aminophenol and acetaminophen, a combination of quinone, chloranil and phenol, a combination of chloranil, phenol and p-aminophenol, a combination of phenol, p-aminophenol and acetaminophen, or a combination of quinone, chloranil, phenol, p-aminophenol and acetaminophen.
Preferably, the concentration of the contaminant in the wastewater is 80ppb to 800ppm, and may be, for example, 80ppb, 200ppb, 500ppb, 1ppm, 50ppm, 100ppm, 200ppm, 300ppm, 400ppm, 500ppm, 600ppm, 700ppm or 800ppm, but is not limited to the recited values, and other values not recited in the numerical ranges are also applicable.
Preferably, the coupling template agent in step (1) is any one or a combination of at least two of organic molecules containing heteroatoms such as O, N, S or P, including amino, thiol, halogen elements and the like.
Preferably, the molar ratio of the coupling templating agent to contaminants in the wastewater in step (1) is (0.1-5):1, and may be, for example, 0.1:1, 0.5:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1 or 5:1, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the oxidation method of step (1) comprises any one or a combination of at least two of aeration oxidation, heating oxidation or oxidant oxidation; typical but non-limiting combinations include aerated oxidation in combination with heated oxidation, heated oxidation in combination with oxidant oxidation, aerated oxidation in combination with oxidant oxidation, or aerated oxidation, heated oxidation in combination with oxidant oxidation.
Preferably, the molar ratio of dissolved oxygen to pollutants in the wastewater in the aerated oxidation is (5-100):1, and may be, for example, 5:1, 10:1, 20:1, 30:1, 40:1, 50:1, 60:1, 70:1, 80:1, 90:1 or 100:1, but is not limited to the recited values, and other values not recited in the numerical ranges are equally applicable; the molar ratio of dissolved oxygen to contaminants in the water is preferably (10-30): 1.
When the molar ratio of the dissolved oxygen to the pollutants in the wastewater is lower than 5:1, the pollutants in the wastewater cannot be directionally reconstructed and oxidized; when the dissolved oxygen is higher than 100:1, the required aeration amount is huge, which is not favorable for the directional reconstruction. Therefore, when the aeration oxidation is selected as the directional reconstruction method, the molar ratio of the dissolved oxygen to the pollutants in the wastewater is (5-100): 1.
Preferably, when the oxidizing agent is used for oxidation, the oxidizing agent comprises any one or a combination of at least two of persulfate, peroxyacetic acid, hydrogen peroxide, fenton reagent, ozone, potassium permanganate or transition metal oxide; typical but non-limiting combinations include combinations of persulfate and peroxyacetic acid, peroxyacetic acid and hydrogen peroxide, hydrogen peroxide and fenton's reagent, fenton's reagent and ozone, ozone and potassium permanganate, potassium permanganate and transition metal oxide, persulfate, peroxyacetic acid and hydrogen peroxide, fenton's reagent and ozone, potassium permanganate and transition metal oxide, or persulfate, peroxyacetic acid, hydrogen peroxide, fenton's reagent, ozone, potassium permanganate and transition metal oxide; transition metal oxides are preferred.
Preferably, the transition metal oxide is MnO2。
Preferably, the molar ratio of the oxidizing agent to the contaminants in the wastewater is (0.2-2):1, and may be, for example, 0.2:1, 0.4:1, 0.5:1, 0.6:1, 0.8:1, 1:1, 1.2:1, 1.5:1, 1.6:1, 1.8:1 or 2:1, but is not limited to the values recited, and other values within the range of values are equally applicable, preferably (0.4-0.8): 1.
When the addition amount of the oxidant is less, the pollutants in the water cannot be sufficiently directionally reconstructed, and the unit molecular dipole moment of the pollutants is not reduced; when the addition amount of the oxidant is large, the cost of directional reconstruction is increased, and new impurities are introduced into water, so that the later treatment is not facilitated.
The flocculating agent used in the flocculation separation in the step (2) comprises any one or a combination of at least two of an inorganic flocculating agent, an organic flocculating agent or a composite flocculating agent.
Preferably, the inorganic flocculant comprises one or a combination of at least two of aluminum salt, polymeric aluminum, iron salt, polymeric iron, polymeric aluminum silicon, polymeric iron silicon, polymeric aluminum iron silicon, titanium salt or polymeric titanium salt; typical but non-limiting combinations include aluminum salts in combination with polyaluminum, polyaluminum in combination with polyferric, polyferric in combination with polyaluminum ferric, polyaluminum ferric in combination with polyaluminum silicon, polyaluminum silicon in combination with polyaluminum ferric silicon, polyaluminum ferric silicon in combination with polyaluminum ferric silicon, titanium salts in combination with polymeric titanium salts.
Preferably, the inorganic flocculant is added in an amount of 2 to 1000mg/L, for example, 2mg/L, 10mg/L, 50mg/L, 100mg/L, 300mg/L, 500mg/L, 600mg/L, 700mg/L, 800mg/L, 900mg/L or 1000mg/L, but not limited to the values listed, and other values not listed in the numerical range are also applicable, preferably 10 to 500 mg/L.
Preferably, the organic flocculant is any one or a combination of at least two of polyacrylamide, polyacrylic acid or polyquaternary ammonium salt and derivatives thereof.
Preferably, the organic flocculant is added in an amount of 0.5-100mg/L, for example, 0.5mg/L, 1mg/L, 2mg/L, 5mg/L, 8mg/L, 10mg/L, 15mg/L, 20mg/L, 30mg/L, 40mg/L, 50mg/L, 60mg/L, 70mg/L, 80mg/L, 90mg/L or 100mg/L, but not limited to the values listed, and other values not listed in the range of values are equally applicable, preferably 2-50 mg/L.
Preferably, the step (2) further comprises a stirring step after the flocculating agent is added, wherein the stirring step comprises a first stirring step and a second stirring step which are sequentially performed.
Preferably, the stirring rate of the first stirring is 100-300r/min, such as 100r/min, 120r/min, 150r/min, 180r/min, 200r/min, 210r/min, 240r/min, 250r/min, 270r/min, 280r/min or 300r/min, but not limited to the enumerated values, and other unrecited values within the numerical range are equally applicable, preferably 150-250 r/min.
Preferably, the first stirring time is 2-8min, such as 2min, 3min, 4min, 5min, 6min, 7min or 8min, but not limited to the recited values, and other values not recited in the numerical range are equally applicable.
Preferably, the second stirring is carried out at a rate of 20 to 80r/min, for example 20r/min, 30r/min, 40r/min, 50r/min, 60r/min, 70r/min or 80r/min, but not limited to the values listed, and other values not listed in the numerical range are equally applicable, preferably 30 to 50 r/min.
Preferably, the second stirring time is 10-30min, for example 10min, 15min, 20min, 25min or 30min, but is not limited to the recited values, and other values not recited in the numerical range are equally applicable.
As a preferred technical scheme of the method, the method comprises the following steps:
(1) directional reconstruction: adding a coupling template agent into the wastewater under an oxidation condition, so that the polymerization degree of the pollutant molecules in the wastewater after directional reconstruction is more than or equal to 20, and the molecular weight reaches more than 3000 Da;
the unit molecular weight of pollutants in the wastewater is less than 200 Da;
the oxidation method comprises any one or the combination of at least two of aeration oxidation, heating oxidation or oxidant oxidation; the mol ratio of dissolved oxygen to pollutants in the wastewater in aeration oxidation is (5-100) to 1; the molar ratio of the oxidant to the pollutants in the wastewater in the oxidation of the oxidant is (0.2-2) to 1;
(2) strengthening and separating: adding a flocculating agent, sequentially carrying out first stirring and second stirring, and carrying out flocculation precipitation on the wastewater obtained in the step (1) to realize solid-liquid separation;
the stirring speed of the first stirring is 100-300r/min, and the time is 2-8 min;
the stirring speed of the second stirring is 20-80r/min, and the time is 10-30 min.
Compared with the prior art, the invention has the beneficial effects that:
the method provided by the invention has strong selectivity to organic pollutants in water, the pollutants in water are cross-coupled by directionally reconstructing the molecules of the pollutants in water, and the pollutants containing amino and/or thiol groups are covalently combined into macromolecular organic matters, so that the electronic distribution of the pollutants is obviously changed, the molecular weight of the pollutants in the wastewater is changed, the solubility of the pollutants in the wastewater is changed, and the pollutants in the wastewater are precipitated; and then, the separation of pollutants in the wastewater is realized in a solid-liquid separation mode.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
Example 1
The embodiment provides a method for strengthening cross-medium resource transformation by directionally reconstructing pollutants in water, which comprises the following steps:
(1) directional reconstruction: adding a coupling template agent into the wastewater under an oxidation condition, so that the polymerization degree of the pollutant molecules in the wastewater after directional reconstruction is more than or equal to 20, and the molecular weight reaches 5000 Da;
the pollutant in the wastewater is 1, 2-benzoquinone, and the concentration is 500 ppm; the coupling template agent is cysteine, and the molar ratio of the added amount of the cysteine to the 1, 2-benzoquinone in the wastewater is 0.1: 1;
the oxidation is carried out by adding manganese dioxide, and the molar ratio of the manganese dioxide to 1, 2-benzoquinone in the wastewater is 0.2: 1;
(2) strengthening and separating: adding a flocculating agent, sequentially carrying out first stirring and second stirring, and carrying out flocculation precipitation on the wastewater obtained in the step (1) to realize solid-liquid separation; the flocculant is polyaluminium chloride, and the dosage is 500 mg/L;
the stirring speed of the first stirring is 200r/min, and the time is 5 min;
the stirring speed of the second stirring is 40r/min, and the time is 20 min.
The TOC in the aqueous solution treated in the step (2) was measured by a TOC analyzer, and the concentration of 1, 2-benzoquinone in the aqueous solution treated in the step (2) was measured by liquid chromatography. The results show that the TOC removal rate was 95.9% and the 1, 2-benzoquinone removal rate was 97.3%.
Example 2
The embodiment provides a method for strengthening cross-medium resource transformation by directionally reconstructing pollutants in water, which comprises the following steps:
(1) directional reconstruction: adding a coupling template agent into the wastewater under an oxidation condition, so that the polymerization degree of the pollutant molecules in the wastewater after directional reconstruction is more than or equal to 20, and the molecular weight reaches 5000 Da;
the pollutant in the wastewater is 1, 2-benzoquinone, and the concentration is 700 ppm; the coupling template agent is cysteine, and the molar ratio of the added amount of the cysteine to 1, 2-benzoquinone in the wastewater is 2: 1;
the oxidation is carried out by adding manganese dioxide, and the molar ratio of the manganese dioxide to 1, 2-benzoquinone in the wastewater is 0.4: 1;
(2) strengthening and separating: adding a flocculating agent, sequentially carrying out first stirring and second stirring, and carrying out flocculation precipitation on the wastewater obtained in the step (1) to realize solid-liquid separation; the flocculating agent is polyferric, and the adding amount is 300 mg/L;
the stirring speed of the first stirring is 150r/min, and the time is 6 min;
the stirring speed of the second stirring is 30r/min, and the time is 25 min.
The TOC in the aqueous solution treated in the step (2) was measured by a TOC analyzer, and the concentration of 1, 2-benzoquinone in the aqueous solution treated in the step (2) was measured by liquid chromatography. The results show that the TOC removal rate was 95.3% and the 1, 2-benzoquinone removal rate was 97.1%.
Example 3
The embodiment provides a method for strengthening cross-medium resource transformation by directionally reconstructing pollutants in water, which comprises the following steps:
(1) directional reconstruction: adding a coupling template agent into the wastewater under an oxidation condition, so that the polymerization degree of the pollutant molecules in the wastewater after directional reconstruction is more than or equal to 20, and the molecular weight reaches 5000 Da;
the pollutant in the wastewater is 1, 2-benzoquinone, and the concentration is 800 ppm; the coupling template agent is cysteine, and the molar ratio of the added amount of the cysteine to 1, 2-benzoquinone in the wastewater is 3: 1;
the oxidation is carried out by adding manganese dioxide, and the molar ratio of the manganese dioxide to 1, 2-benzoquinone in the wastewater is 0.6: 1;
(2) strengthening and separating: adding a flocculating agent, sequentially carrying out first stirring and second stirring, and carrying out flocculation precipitation on the wastewater obtained in the step (1) to realize solid-liquid separation; the flocculant is polyaluminum ferric chloride, and the dosage is 1000 mg/L;
the stirring speed of the first stirring is 250r/min, and the time is 3 min;
the stirring speed of the second stirring is 60r/min, and the time is 15 min.
The TOC in the aqueous solution treated in the step (2) was measured by a TOC analyzer, and the concentration of 1, 2-benzoquinone in the aqueous solution treated in the step (2) was measured by liquid chromatography. The results show that the TOC removal rate was 95.6% and the 1, 2-benzoquinone removal rate was 97.8%.
Example 4
The embodiment provides a method for strengthening cross-medium resource transformation by directionally reconstructing pollutants in water, which comprises the following steps:
(1) directional reconstruction: adding a coupling template agent into the wastewater under an oxidation condition, so that the polymerization degree of the pollutant molecules in the wastewater after directional reconstruction is more than or equal to 20, and the molecular weight reaches 5000 Da;
the pollutant in the wastewater is 1, 2-benzoquinone, and the concentration is 200 ppm; the coupling template agent is cysteine, and the molar ratio of the added amount of the cysteine to 1, 2-benzoquinone in the wastewater is 5: 1;
the oxidation is carried out by adding manganese dioxide, and the molar ratio of the manganese dioxide to 1, 2-benzoquinone in the wastewater is 0.8: 1;
(2) strengthening and separating: adding a flocculating agent, sequentially carrying out first stirring and second stirring, and carrying out flocculation precipitation on the wastewater obtained in the step (1) to realize solid-liquid separation; the flocculating agent is polymeric aluminum ferric silicate, and the adding amount is 100 mg/L;
the stirring speed of the first stirring is 100r/min, and the time is 8 min;
the stirring speed of the second stirring is 20r/min, and the time is 30 min.
The TOC in the aqueous solution treated in the step (2) was measured by a TOC analyzer, and the concentration of 1, 2-benzoquinone in the aqueous solution treated in the step (2) was measured by liquid chromatography. The results show that the TOC removal rate was 94.9% and the 1, 2-benzoquinone removal rate was 96.6%.
Example 5
The embodiment provides a method for strengthening cross-medium resource transformation by directionally reconstructing pollutants in water, which comprises the following steps:
(1) directional reconstruction: adding a coupling template agent into the wastewater under an oxidation condition, so that the polymerization degree of the pollutant molecules in the wastewater after directional reconstruction is more than or equal to 20, and the molecular weight reaches 5000 Da;
the pollutant in the wastewater is 1, 2-benzoquinone, and the concentration is 500 ppm; the coupling template agent is cysteine, and the molar ratio of the added amount of the cysteine to 1, 2-benzoquinone in the wastewater is 4: 1;
the oxidation is carried out by adding manganese dioxide, and the molar ratio of the manganese dioxide to 1, 2-benzoquinone in the wastewater is 2: 1;
(2) strengthening and separating: adding a flocculating agent, sequentially carrying out first stirring and second stirring, and carrying out flocculation precipitation on the wastewater obtained in the step (1) to realize solid-liquid separation; the flocculant is polyacrylamide, and the dosage is 30 mg/L;
the stirring speed of the first stirring is 300r/min, and the time is 2 min;
the stirring speed of the second stirring is 80r/min, and the time is 10 min.
The TOC in the aqueous solution treated in the step (2) was measured by a TOC analyzer, and the concentration of 1, 2-benzoquinone in the aqueous solution treated in the step (2) was measured by liquid chromatography. The results show that the TOC removal rate is 96.1% and the 1, 2-benzoquinone removal rate is 98.0%.
Example 6
This example provides a method for the directional reconstitution of contaminants in water to enhance cross-media resource conversion, which is the same as example 5 except that the manganese dioxide in step (1) is replaced with an equimolar amount of sodium persulfate.
The TOC in the aqueous solution treated in the step (2) was measured by a TOC analyzer, and the concentration of 1, 2-benzoquinone in the aqueous solution treated in the step (2) was measured by liquid chromatography. The results show that the TOC removal rate was 94.5% and the 1, 2-benzoquinone removal rate was 95.6%.
Example 7
This example provides a method for the directional reconstitution of contaminants in water to enhance cross-media resource conversion, which is the same as example 5 except that the manganese dioxide of step (1) is replaced with an equimolar amount of peroxyacetic acid.
The TOC in the aqueous solution treated in the step (2) was measured by a TOC analyzer, and the concentration of 1, 2-benzoquinone in the aqueous solution treated in the step (2) was measured by liquid chromatography. The results show that the TOC removal rate was 94.3% and the 1, 2-benzoquinone removal rate was 95.9%.
Example 8
This example provides a method for directional reconstruction of pollutants in water to enhance cross-media resource transformation, which is the same as example 5 except that the oxidation is aeration oxidation, and the molar ratio of dissolved oxygen to 1, 2-benzoquinone in wastewater in aeration oxidation is 20: 1.
The TOC in the aqueous solution treated in the step (2) was measured by a TOC analyzer, and the concentration of 1, 2-benzoquinone in the aqueous solution treated in the step (2) was measured by liquid chromatography. The results show that the TOC removal rate was 90.2% and the 1, 2-benzoquinone removal rate was 93.7%.
Example 9
This example provides a method for directional reconstruction of pollutants in water to enhance cross-media resource transformation, which is the same as example 5 except that the oxidation is aeration oxidation, and the molar ratio of dissolved oxygen to 1, 2-benzoquinone in wastewater in aeration oxidation is 100: 1.
The TOC in the aqueous solution treated in the step (2) was measured by a TOC analyzer, and the concentration of 1, 2-benzoquinone in the aqueous solution treated in the step (2) was measured by liquid chromatography. The results show that the TOC removal rate was 92.5% and the 1, 2-benzoquinone removal rate was 94.4%.
Example 10
This example provides a method for directional reconstruction of pollutants in water to enhance cross-media resource transformation, which is the same as example 5 except that the oxidation is aeration oxidation, and the molar ratio of dissolved oxygen to 1, 2-benzoquinone in wastewater in aeration oxidation is 5: 1.
The TOC in the aqueous solution treated in the step (2) was measured by a TOC analyzer, and the concentration of 1, 2-benzoquinone in the aqueous solution treated in the step (2) was measured by liquid chromatography. The results show that the TOC removal rate was 88.5% and the 1, 2-benzoquinone removal rate was 90.1%.
Example 11
The embodiment provides a method for strengthening cross-medium resource transformation by directionally reconstructing pollutants in water, which comprises the following steps:
(1) directional reconstruction: adding a coupling template agent into the wastewater under an oxidation condition, so that the polymerization degree of the pollutant molecules in the wastewater after directional reconstruction is more than or equal to 20, and the molecular weight reaches 5000 Da;
the pollutant in the wastewater is 1, 4-benzoquinone, and the concentration is 500 ppm; the coupling template agent is glutathione, and the molar ratio of the added amount of the glutathione to 1, 4-benzoquinone in the wastewater is 4: 1;
the oxidation is carried out by adding manganese dioxide, and the molar ratio of the manganese dioxide to 1, 4-benzoquinone in the wastewater is 2: 1;
(2) strengthening and separating: adding a flocculating agent, sequentially carrying out first stirring and second stirring, and carrying out flocculation precipitation on the wastewater obtained in the step (1) to realize solid-liquid separation; the flocculant is polyaluminium chloride, and the dosage is 500 mg/L;
the stirring speed of the first stirring is 300r/min, and the time is 2 min;
the stirring speed of the second stirring is 80r/min, and the time is 10 min.
The TOC in the aqueous solution treated in the step (2) was measured by a TOC analyzer, and the concentration of 1, 4-benzoquinone in the aqueous solution treated in the step (2) was measured by liquid chromatography. The results show that the TOC removal rate was 94.3% and the 1, 4-benzoquinone removal rate was 95.2%.
Example 12
The embodiment provides a method for strengthening cross-medium resource transformation by directionally reconstructing pollutants in water, which comprises the following steps:
(1) directional reconstruction: adding a coupling template agent into the wastewater under an oxidation condition, so that the polymerization degree of the pollutant molecules in the wastewater after directional reconstruction is more than or equal to 20, and the molecular weight reaches 5000 Da;
the pollutant in the wastewater is 2-chloro-1, 4-benzoquinone, and the concentration is 200 ppb; the coupling template agent is glutathione, and the molar ratio of the added amount of the glutathione to the 2-chloro-1, 4-benzoquinone in the wastewater is 4: 1;
the oxidation is carried out by adding manganese dioxide, and the molar ratio of the manganese dioxide to the 2-chloro-1, 4-benzoquinone in the wastewater is 2: 1;
(2) strengthening and separating: adding a flocculating agent, sequentially carrying out first stirring and second stirring, and carrying out flocculation precipitation on the wastewater obtained in the step (1) to realize solid-liquid separation; the flocculant is polyaluminium chloride, and the dosage is 5 mg/L;
the stirring speed of the first stirring is 300r/min, and the time is 2 min;
the stirring speed of the second stirring is 80r/min, and the time is 10 min.
The TOC in the aqueous solution treated in the step (2) was measured by a TOC analyzer, and the concentration of 2-chloro-1, 4-benzoquinone in the aqueous solution treated in the step (2) was measured by liquid chromatography. The results show that the TOC removal rate was 95.8% and the removal rate of 2-chloro-1, 4-benzoquinone was 92.7%.
Example 13
The embodiment provides a method for strengthening cross-medium resource transformation by directionally reconstructing pollutants in water, which comprises the following steps:
(1) directional reconstruction: adding a coupling template agent into the wastewater under an oxidation condition, so that the polymerization degree of the pollutant molecules in the wastewater after directional reconstruction is more than or equal to 20, and the molecular weight reaches 5000 Da;
the pollutant in the wastewater is 2, 6-dichloro-1, 4-benzoquinone, and the concentration is 200 ppb; the coupling template agent is glutathione, and the molar ratio of the added amount of the glutathione to the 2, 6-dichloro-1, 4-benzoquinone in the wastewater is 4: 1;
the oxidation is carried out by adding manganese dioxide, and the molar ratio of the manganese dioxide to the 2, 6-dichloro-1, 4-benzoquinone in the wastewater is 2: 1;
(2) strengthening and separating: adding a flocculating agent, sequentially carrying out first stirring and second stirring, and carrying out flocculation precipitation on the wastewater obtained in the step (1) to realize solid-liquid separation; the flocculating agent is polyacrylic acid, and the adding amount is 5 mg/L;
the stirring speed of the first stirring is 300r/min, and the time is 2 min;
the stirring speed of the second stirring is 80r/min, and the time is 10 min.
The TOC in the aqueous solution treated in the step (2) was measured by a TOC analyzer, and the concentration of 2, 6-dichloro-1, 4-benzoquinone in the aqueous solution treated in the step (2) was measured by liquid chromatography. The results show that the TOC removal rate was 95.1% and the removal rate of 2, 6-dichloro-1, 4-benzoquinone was 94.6%.
Example 14
The embodiment provides a method for directionally reconstructing pollutants in water to strengthen cross-medium resource transformation, which is the same as the embodiment 5 except that the stirring speeds of the first stirring and the second stirring are both 300 r/min.
And the stirring speed of the second stirring is higher, so that the floccule can not grow up fully, and the flocculation precipitation of the product after the directional reconstruction is difficult to realize.
Example 15
The embodiment provides a method for directionally reconstructing pollutants in water to strengthen cross-medium resource transformation, which is the same as the embodiment 5 except that the stirring speeds of the first stirring and the second stirring are both 80 r/min.
Because the stirring speed of the first stirring is slow, the product after the directional reconstruction cannot be rapidly destabilized, so that effective solid-liquid separation cannot be realized, and the removal effect of pollutants is poor.
Comparative example 1
The comparative example provides a method for directionally reconstructing pollutants in water to strengthen cross-medium resource transformation, and the method is the same as the method in the example 5 except that the coupling template agent cysteine is not added.
Since the directional reconstitution effect of 1, 2-benzoquinone was poor without the addition of a coupling template agent, and efficient polymerization of 1, 2-benzoquinone could not be achieved, the TOC in the aqueous solution treated in step (2) was measured using a TOC analyzer, and the concentration of 1, 2-benzoquinone in the aqueous solution treated in step (2) was measured using liquid chromatography, and it was found that the TOC removal rate was only 17.6% and the removal rate of 1, 2-benzoquinone was only 15.9%.
Comparative example 2
The comparative example provides a method for directionally reconstructing pollutants in water to strengthen cross-medium resource transformation, and the method is the same as the method in the example 5 except that the flocculating agent polyacrylamide is not added.
Since the flocculant is not added, the solid-liquid separation effect is poor after the oriented reconstitution of the 1, 2-benzoquinone, and the effective sedimentation of the 1, 2-benzoquinone cannot be realized, the TOC in the aqueous solution treated in the step (2) is measured by using a TOC analyzer, and the concentration of the 1, 2-benzoquinone in the aqueous solution treated in the step (2) is measured by using a liquid chromatography, and the obtained results show that the TOC removal rate is only 59.8% and the removal rate of the 1, 2-benzoquinone is 98.0%.
Comparative example 3
The comparative example provides a method for directionally reconstructing pollutants in water to strengthen cross-medium resource conversion, and the method is the same as the method in the example 5 except that the solution contains organic solvent ethanol, so that the total TOC content is 8000 ppm.
Because a large amount of organic solvent contained in the solution can not be subjected to polymerization coupling reaction under the oxidation condition, the flocculation precipitation effect of the organic solvent in the solution can not be enhanced by directional reconstruction, only 1, 2-benzoquinone can be effectively precipitated through the coupling reaction of the 1, 2-benzoquinone, the TOC in the aqueous solution treated in the step (2) is measured by using a TOC analyzer, and the concentration of the 1, 2-benzoquinone in the aqueous solution treated in the step (2) is measured by using a liquid chromatography. As a result, it was found that the removal rate of 1, 2-benzoquinone was 98.0%, but the removal rate of TOC was 5% or less.
In conclusion, the method provided by the invention has strong selectivity on organic pollutants in water, through directionally reconstructing pollutant molecules in water, the pollutants in water are cross-coupled and are easy to be oxidized into quinone substances, and the pollutants are covalently combined into macromolecular organic matters, so that the electronic distribution of the pollutants is obviously changed, the molecular weight of the pollutants is obviously increased, the subsequent solid-liquid separation efficiency is improved, and finally, the pollutants in water are removed through solid-liquid separation.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A wastewater directional reconstruction-reinforced separation coupling method is characterized by comprising the following steps:
(1) directional reconstruction: adding a coupling template agent into the wastewater under an oxidation condition to directionally reconstruct pollutant molecules in the wastewater to a molecular weight of more than 3000 Da;
(2) strengthening and separating: and (3) adding a flocculating agent, and performing flocculation precipitation on the wastewater obtained in the step (1) to realize solid-liquid separation.
2. The method of claim 1, wherein the molecular weight of contaminants in the wastewater of step (1) does not exceed 200 Da.
3. The method according to claim 1 or 2, wherein the coupling template agent in step (1) is any one or a combination of at least two of organic molecules containing heteroatoms such as O, N, S or P, including amino groups, thiols and halogen elements;
preferably, the molar ratio of the coupling template agent in the step (1) to the pollutants in the wastewater is (0.1-5): 1.
4. A process according to any one of claims 1 to 3, wherein the oxidation in step (1) comprises any one or a combination of at least two of aerated oxidation, heated oxidation or oxidant oxidation, preferably oxidant oxidation.
5. The method according to claim 4, wherein the molar ratio of dissolved oxygen to pollutants in the wastewater in the aeration oxidation is (5-100):1, preferably (10-30): 1.
6. The method according to claim 4, wherein the oxidizing agent is any one or a combination of at least two of persulfate, peroxyacetic acid, hydrogen peroxide, Fenton's reagent, ozone, potassium permanganate or transition metal oxide, preferably transition metal oxide;
preferably, the transition metal oxide is MnO2。
7. The method according to claim 6, characterized in that the molar ratio of the oxidizing agent to the pollutants in the wastewater is (0.2-2):1, preferably (0.4-0.8): 1.
8. The method according to any one of claims 1 to 7, wherein the flocculant of step (2) is selected from one or a combination of at least two of an inorganic flocculant, an organic flocculant or an inorganic-organic composite flocculant;
preferably, the inorganic flocculant comprises one or a combination of at least two of aluminum salt, polymeric aluminum, iron salt, polymeric iron, polymeric aluminum silicon, polymeric iron silicon, polymeric aluminum iron silicon, titanium salt or polymeric titanium salt;
preferably, the dosage of the inorganic flocculant is 2-1000mg/L, preferably 10-500 mg/L;
preferably, the organic flocculant is any one or a combination of at least two of polyacrylamide, polyacrylic acid or polyquaternary ammonium salt and derivatives thereof;
preferably, the dosage of the organic flocculant is 0.5-100mg/L, preferably 2-50 mg/L.
9. The method according to claim 8, characterized in that the step (2) of adding the flocculating agent is followed by a step of stirring, wherein the stirring is a first stirring and a second stirring which are sequentially carried out;
preferably, the stirring speed of the first stirring is 100-300r/min, preferably 150-250 r/min;
preferably, the stirring time of the first stirring is 2-8min, preferably 4-6 min;
preferably, the stirring speed of the second stirring is 20-80r/min, preferably 30-50 r/min;
preferably, the stirring time of the second stirring is 10 to 30min, preferably 15 to 25 min.
10. A method according to any of claims 1-9, characterized in that the method comprises the steps of:
(1) directional reconstruction: adding a coupling template agent into the wastewater under an oxidation condition, so that the polymerization degree of the pollutant molecules in the wastewater after directional reconstruction is more than or equal to 20, and the molecular weight reaches more than 3000 Da;
the unit molecular weight of pollutants in the wastewater is less than 200 Da;
the oxidation method comprises any one or the combination of at least two of aeration oxidation, heating oxidation or oxidant oxidation; the mol ratio of dissolved oxygen to pollutants in the wastewater in aeration oxidation is (5-100) to 1; the molar ratio of the oxidant to the pollutants in the wastewater in the oxidation of the oxidant is (0.2-2) to 1;
(2) strengthening and separating: adding a flocculating agent, sequentially carrying out first stirring and second stirring, and carrying out flocculation precipitation on the wastewater obtained in the step (1) to realize solid-liquid separation;
the stirring speed of the first stirring is 100-300r/min, and the time is 2-8 min;
the stirring speed of the second stirring is 20-80r/min, and the time is 10-30 min.
CN202011119853.9A 2020-10-19 2020-10-19 Wastewater directional reconstruction-reinforced separation coupling method Pending CN112142232A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014005320A1 (en) * 2012-07-06 2014-01-09 Empire Technology Development Llc Molecularly imprinted catalysts and methods of making and using the same
CN103708673A (en) * 2013-11-29 2014-04-09 中国科学院过程工程研究所 Method for removing trace amount of toxic pollutants in water by enzyme-loading magnetic particle reinforced flocculation
CN105964217A (en) * 2016-06-17 2016-09-28 中国科学院城市环境研究所 Preparation method of magnetic KMS-1/Fe3O4 composite material and application of material for removing ciprofloxacin

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014005320A1 (en) * 2012-07-06 2014-01-09 Empire Technology Development Llc Molecularly imprinted catalysts and methods of making and using the same
CN103708673A (en) * 2013-11-29 2014-04-09 中国科学院过程工程研究所 Method for removing trace amount of toxic pollutants in water by enzyme-loading magnetic particle reinforced flocculation
CN105964217A (en) * 2016-06-17 2016-09-28 中国科学院城市环境研究所 Preparation method of magnetic KMS-1/Fe3O4 composite material and application of material for removing ciprofloxacin

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DU PENGHUI ET AL.: "Transformation of halobenzoquinones with the presence of amino acids in water: Products, pathways and toxicity", 《WATER RESEARCH》 *
ZHONG CHEN ET AL.,: "Polymerization of micropollutants in natural aquatic environments: A review", 《SCIENCE OF THE TOTAL ENVIRONMENT》 *
杜朋辉: "水中新兴有机污染物的聚合偶联机理研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 *

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